3,3-dichloro-2-oxopolymethylenimines

ABSTRACT

THE INVENTION RELATES TO 3,3-DICHLORO-2-OXOPOLYMETHYLENIMINES AND BIS(3,3 - DICHLORO - 2 - OXOPOLYMETHYLENEIMINES) HAVING USEFUL ANTI-INFLAMMATORY PROPERTIES AS DETERMINED BY THEIR INHIBITION OF CARRAGEENAN INDUCED EDEMA IN RATS.

United States Patent 3,708,473 3,3-DICHLOR0-2-OXOPOLYMETHYLENIMINES Joseph C. Collins, East Greenbush, N.Y., assignor to Sterling Drug Inc., New York, N.Y.

No Drawing. Continuation-impart of application Ser. No. 862,084, Sept. 29, 1969, which is a continuation-in-part of application Ser. No. 673,926, Oct. 9, 1967. This aplication Feb. 8, 1971, Ser. No. 113,669

Int. Cl. C07d 41/06 US. Cl. 260-239.3 R 21 Claims ABSTRACT OF THE DISCLOSURE The invention relates to 3,3-dichloro-2-oxopolymethylenimines and bis(3,3 dichloro 2 oxopolymethylenimines) having useful anti-inflammatory properties as determined by their inhibition of carrageenan induced edema in rats.

This application is a continuation-in-part of copending application, Ser. No. 862,084, filed Sept. 29, 1969, now US. Patent 3,647,782, issued Mar. 7, 1972, which is in turn a continuation-in-part of prior copending application, Ser. No. 673,926, filed Oct. 9, 1967, now US. Pat. 3,549,- 654, issued Dec. 22, 1970.

This invention relates to 3,3-dichloro-2-oxopolymethylenimine derivatives and bis(3,3-dich1oro-2-oxopolymethylenirnine) derivatives.

According to one aspect of the invention there is provided the compounds having the Formula I where R is one of the group consisting of phenyl-loweralkyl, 3-indolyl-lower-alkyl, phenyl, naphthyl, 5,6,7,8- tetrahydronaphthyl, fluorenyl, 9-oxofluorenyl, pyridyl, pyrimidinyl and benzothiazolyl radicals, and such radicals substituted by from one to three inclusive substituents of the group consisting of halo, lower-alkyl, phenyllower-alkylmercapto, loWer-alkylsulfonyl, trihalomethyl, trifluoromethoxy, nitro, di(lower-alkyl)amino, lower-alkafluoromethoxy, nitro, di(lower-alkyl)amino, lower-alkanoylamino, amino, lower-alkanoyloxy and hydroXy; and n is an integer from 1 to 3 inclusive.

In the compounds of the invention having the Formula I above, when the radicals represented by R are substituted, as described hereinabove, the substituents can be attached at any of the available positions of the carbocyclic or heterocyclic rings of such radicals and Where there are a plurality of substituents, such substituents can be the same or different and they can be in any of the various position combinations relative to each other.

According to another aspect of the invention there is provided the compounds having the Formula II 0 Cll C1 N-NB where NB is one of the group consisting of l-pyrrolidinyl, l-piperidinyl, 4-loWer-alkyl-l-piperazinyl, 4 benzyl-l-piperazinyl, 4-phenyl-l-piperazinyl, 4-morpholinyl and 4- thiomorpholinyl, or NB is 'NRR" where R and R", Which can be the same or different, are lower-alkyl, benzyl, phenyl, or phenyl substituted by from one to three inclusive substituents of the group consisting of halo, lower-alkyl, loWer-alkoxy, trihalomethyl and nitro; and n is an integer from 1 to 3 inclusive.

In the compounds of Formula II above, when phenyl is substituted, as described above, the substituents can be attached to any of the available positions of the phenyl ring and Where there are a plurality of substituents, such substituents can be the same or dilferent and they can be in any of the various position combinations relative to each other.

According to another aspect of the invention, claimed in copending application Ser. No. 862,084, there is provided the compounds having the Formula III (CH2)n- III Where Ar is phenylene, biphenylylene, or phenylene or biphenylylene substituted by from one to three substituents of the group consisting of halo, lower-alkyl, phenyl-loweralkyl, lower-alkoxy, phenyl-lower-alkoxy, phenoxy, loweralkylmercapto, lower-alkylsulfonyl, trihalomethyl, nitro, di(loWer-alkyl)aniino, lower-alkanoylamino, amino, loweralkanoyloxy, and hydroxy; m is a number from 0 to 3 inclusive; and n is an integer from 1 to 3 inclusive.

In the compounds of the invention having the Formula III above, when phenylene or biphenylylene, represented by Ar, are substituted, as described hereinabove, by more than one substituent, such substituents can be the same or different and they can be in any of the various position combinations relative to each other.

According to another aspect of the invention there is provided the compounds having the Formula IV Where Y is alkylene having from two to twelve carbon atoms, and n is an integer from 1 to 3. Compounds having the Formula IV, Where n is 1, are claimed in US. Pat. 3,549,654.

According to yet another aspect of the invention there is provided the compounds having the Formula IA Where Q is trihalomethyl or trifluoromethoxy and Q is hydrogen, halo or trihalomethyl; and n is an integer from 1 to 3 inclusive.

The compounds having the Formula IA are useful as intermediates in the preparation of compounds of this invention falling within the scope of Formula I.

In the compounds of the invention having Formula IA above, the substituents Q and Q can be attached to the phenyl ring at any of the available positions and can be in any of the position combinations relative to each other.

In Formula I above where R is phenyl-lower-alkyl or phenyl-lower-alkyl substituted as hereinbefore defined for the radicals represented by R, the term phenyl-loweralkyl means a group wherein lower-alkyl contains from one to six carbon atoms which can be arranged as straight or branched chains, which without limiting the generality of the foregoing is illustrated by phenylmethyl, Z-phenyll-ethyl, 3-phenyl-l-propyl, Z-phenyl-l-propyl, 4-phenyl-1- butyl, 4 phenyl 2 butyl, S-phenyl-l-amyl, 6-phenyl-lhexyl, and the like.

In Formula I above where R is 3-indolyl-lower-alkyl or 3 indolyl-lower-alkyl substituted as hereinbefore defined for the radicals represented by R, the term 3- indolyl-lower alkyl means a group wherein lower-alkyl contains from one to three carbon atoms which can be arranged as straight or branched chains, which without limiting the generality of the foregoing is illustrated by (3- indolyl)methyl, 2-(3-indolyl)-l-ethyl, 3 (3 indolyl) 1- propyl, 2-(3-indolyl)-1-propyl, and the like.

The divalent aromatic radicals as represented by Ar in Formula I-II can have each of their two connecting linkages bound to any available carbon atom of the aromatic rings such that they can be in any of the various position combinations relative to each other.

In the above Formula III, when m is 0, the nitrogen atoms are each linked directly to a ring carbon atom of the radicals represented by Ar.

In the above Formula III, Where m is a number from 1 to 3 inclusive, C H represents lower-alkylene as illustrated by -CH --CH CH CH CH CH -CI-I(CH )CH In Formula IV above, Y represents alkylene having its connecting linkages on different carbon atoms as illustrated by CH CH -CH CH CH -(CH 2)5 2)6, 2)8 2)1o z)12, 3) z-, 3)2 z and the like.

The term halo, as used hereinabove and throughout this specification, includes chloro, bromo, iodo and fluoro.

The terms lower-alkyl, lower-alkanoyloxy, loweralkanoy and lower-alkoxy, as used hereinabove and throughout this specification, mean such groups preferably containing from one to six carbon atoms which can be arranged as straight or branched chains, and without limiting the generality of the foregoing, are illustrated by methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, hexyl, acetoxy, propionoxy, trimethylacetoxy, acetyl, propionyl, trimethyl-acetyl, methoxy, ethoxy, isobutoxy, and the like.

The novel compounds of the invention, represented by Formulas I, H, HI and IV above, are prepared by cyclization of the corresponding w-chloroalkanoic acid amides having the Formulas VA and VB, w-chloroalkanoic acid hydrazides having the Formulas VIA and VIB, and bis (w-chloroalkanoic acid amides) having the Formulas IXA and IXB and the Formulas XIA and XIB and further reacting the resulting cyclized compounds of Formulas VIIB, VIIIB, XB, and XIIB With a chlorinating agent so as to dichlorinate the ring carbon atom vicinal to each ring carbonyl group,

XIIB

where R, NB, Ar, m and n, and Y have the meaning hereinbefore defined for R of Formula I; NE of Formula II; Ar, m and n of Formula III; and Y of Formula IV respectively, except that the radicals represented by R and Ar cannot bear amino and/or hydroxy substituents, such substituents being introduced as described hereinbelow.

The cyclization reaction is advantageously performed in a suitable solvent in the presence of at least a stoichiometric amount of an acid-acceptor and in a temperature range of from about 5 C. to C.

The cyclization of the w-chloroalkanoic acid amides of Formula VA and Formula VB where n is a number from 1 to 2 inclusive, the w-chloroalkanoic acid hydrazides oi Formula VIA and Formula VIB Where n is a number from 1 to 2 inclusive and the bis(w-chloroalkanoic acid amides) of Formulas IXA and XIA and Formulas IXB and XIB where n is a number from 1 to 2 inclusive is preferably carried out at room temperature in methyl or ethyl alcohol in the presence of a stoichiometric amount or slight excess of sodium hydroxide.

The cyclization of the w-chloroalkanoic acid amides of Formula VB where n is the number 3 and the wchloroalkanoic acid hydrazides of Formula VI-B, Where it is the number 3 and the bis(w-chloroalkanoic acid amides) of Formulas IXB and XIB, where n is the number 3, is preferably carried out in dimethyl sulfoxide in the presence of a stoichiometric amount or slight excess of potassium tert-butoxide at a temperature of from about 20 C. to 80 C.

The compounds of Formula VIIB, Formula VIIIB, Formula XB and Formula XIIB can be converted to the corresponding compounds of Formula I, Formula II, Formula III and Formula IV respectively by reaction in a suitable solvent, e.g., xylene, benzene or chloroform, with a suitable chlorinating agent, e.g., chlorine gas in the presence of either phosphorus trichloride or phosphorus pentachloricle; sulfuryl chloride in the presence of posphorus pentachloride; or phosphorus pentachloride. Depending on the chlorinating agent and solvent used the reaction temperature can range from about to 120 C. and the reaction time can range from about onehalf hour to about twenty-four hours. The preferred reaction is carried out with at least one equivalent of phosphorus pentachloride. The reaction is conveniently carried out by suspending three to four equivalents of phosphorus pentachloride in a suitable solvent, adding a solution of the appropriate 2-oxocyclomethylenimine or bis(2 oxocyclomethylenimine) in a suitable solvent and finally heating in the range of about 50 to about 100 C. The following general procedure illustrates the preferred method:

A solution of the appropriate 2 oxocyclomethylenlimine derivative (0.10 mole) or bis(2-oxocyclomethylenimine) (0.10 mole) in 150 ml. xylene is added dropwise during one hour to a stirred suspension of three equivalents of phosphorus pentachloride in 200 ml. xylene at room temperature. The mixture is heated during one hour to 80 to 90 C. and heating is continued for onehalf hour. The mixture is evaporated to dryness under reduced pressure and the residue is stirred with excess aqueous sodium carbonate solution. The resulting insoluble material is collected and recrystallized from a suitable solvent to give the corresponding 3,3-dichloro-2- oxo-polymethylenimine derivative, or bis(3,3-dichloro-2- oxopolymethylenimine) respectively.

The intermediate w-chloroalkanoic acid amides having the Formulas VA and VB, w-chloroalkanoic acid hydrazides VIA and VIB, and the bis(w-chloroalkanoic acid amides) having the Formulas IXA, IXB, XIA and XIB are prepared by reacting the corresponding amines having the Formula R-NH (XIII), hydrazines having the Formula H N NB (XIV) and di-amines having the Formulas H N(C H2m)-Ar-(C H )NH (XV) and H -NY-NH (XVI), Where R, NB, Ar and m, and Y have the meaning hereinbefore defined for R of Formula VA; NB of Formula II; Ar and m of Formula IXA; and Y of Formula IV respectively, which belong to known classes of compounds, with the appropriate amount of the known acid chloride, 2,2,4-trichlorobutyryl chloride, or the known acid chloride having the Formula ClCH (CH CH COCl (XVII), where n is the number from 1 to 3 inclusive, that is, 4-chlorobutyryl chloride, 5 chlorovaleryl chloride and 6-chlorohexanoyl chloride, in a suitable solvent in the presence of at least a stoichiometric amount of an acid-acceptor such as sodium hydroxide, sodium carbonate, or triethylamine and at a temperature ranging from about 0 to 25 C.

The reaction is preferably carried out by dissolving an appropriate amine having the Formula XIII, hydrazine having the Formula XIV, or di-amine having the Formula XV or XVI, in benzene, methylene dichloride or ethylene dichloride, adding an excess of triethylamine or a stoichiometric amount of aqueous sodium carbonate or sodium hydroxide, cooling to 5 to 10 C., and gradually adding a stoichiometric amount or slight excess of the appropriate acid chloride.

The compounds of Formula I where the radicals represented by R are substituted by one or more amino and/or hydroxy substituents, and the compounds of Formula III where Ar is substituted by one or more amino and/or hydroxy substituents are prepared, by well known hydrolysis procedures, from the corresponding compounds where the radicals represented by R and Ar are substituted by one or more lower-alkanoylamino and/or lower-alkanoyloxy substituents, whereby said substituents are converted to amino and/or hydroxy substituents.

In the case of a lower-alkanolyamino substituent, e.g. an acetamido substituent, the hydrolysis can be carried out at room temperature in ether containing an amount of hydrogen chloride slightly in excess of one equivalent. The amine hydrochloride salt so obtained can be converted to the corresponding free base by neutralization with an equivalent of a suitable acid acceptor.

In the case of a lower-alkanoyloxy substituent, e.g. acetoxy substituent, the hydrolysis can be carried out at room temperature in aqueous methyl alcohol containing an amountof potassium hydroxide slightly in excess of one equivalent.

The hydrazines having the Formula XIV are known compounds or are readily prepared from well known, readily available amines having the Formula XVIII (H-N-B) by standard procedures, e.g. b-y nitrosation followed by reduction of the N-nitroso intermediate so obtained.

The following general procedure exemplifies the method:

To a vigorously stirred solution of one mole of amine (HNB, XVIII) in 145 ml. concentrated hydrochloric acid and 400 g. ice-water is added a solution of one mole sodium nitrite in 250 ml. water during ten minutes, while the reaction temperature is maintained below 10 C. and stirring is continued one hour. The reaction mixture is extracted with a suitable solvent, e.g. benzene and the extract is evaporated to dryness under reduced pressure. The crude N-nitroso compound (ON-NB, XIX) can be purified if desired by well known procedures, e.g. by distillation under reduced pressure or recrystallization. To a vigorously stirred mixture of 4.3 g.-atoms of zinc dust in 400 ml. water is added slowly a solution of one mole of the N-nitroso compound in 4.8 moles glacial acetic acid during two hours while the reaction temperature is maintained at 1-0 to 20 C. Stirring is continued for one hour and the mixture then is warmed to about C. and filtered; The cooled filtrate is treated with an amount of 40% aqueous sodium hydroxide suflicient to redissolve the precipitated zinc hydroxide and then extracted with a suitable solvent, e.g. ether. The extract is evaporated to dryness and the crude product is purified by well known procedures to give the hydrazine of Formula XIV (H NNB).

The compounds of the invention, having the Formulas I, II, III and IV above, are therapeutically active substances which possess useful anti-inflammatory properties. The actual determination of the numerical biological data definitive for a particular compound is readily determined by standard test procedures by technicians having ordinary skill in pharmacological test procedures, without the need for any extensive experimentation.

The anti-inflammatory activity of the compounds of the invention having the Formulas I, II, III and IV above, was determined in the carrageenan edema test [Winter et al., Proc. Soc. Exp. Biol. Med. 111, 544-547 (1962)] wherein the test agents were administered orally in multiple doses to fasted male albino rats. One hour after medication five hundredths of one ml. of 0.75% carrageenan was injected into the foot of each rat and three hours after the injections of carrageenan the weight of the foot edema was determined. The calculated difierence between the average weight of the control and medicated rats was used as a measure of the degree of inhibition of carrageenan edema due to the administration of the test agent. Consistent, significant inhibition of carrageenan edema was found when the compounds of this invention were administered orally at doses ranging from 25 to 400 mg./kg.

The compounds having the Formulas I, II, III and IV above, can be prepared for use by conventional pharmaceutical procedures; that is, in an aqueous or oil suspension in a pharmaceutically acceptable vehicle (aqueous alcohol, glycol, oil solution, or oil-water emulsion) for parenteral or oral administration; in capsule or tablet form with conventional excipients (for example, calcium carbonate, starch, lactose, talc, magnesium stearate, gum acacia, and the like) for oral administration.

The molecular structures of the compounds of the invention were assigned on the basis of the method of their synthesis and study of their infrared spectra, and confirmed by the correspondence between calculated and found values for the elementary analysis for representative examples.

The invention is illustrated by, but is not limited to, the following examples:

EXAMPLE 1.METHOD l (A) N- (4-chlorophenyl -2,2,4-trichlorobutyrarnide To a stirred, ice-cooled mixture of 4.2 g. sodium hydroxide in 100 ml. water and 12.7 g. 4-chloroaniline in 200 ml. ethylene dichloride was added 21 g. 2,2,4-trichlorobutyryl chloride during fifteen minutes. The mixture was stirred for one-half hour and the precipitate was filtered and washed with water. The filtrate was washed with dilute aqueous hydrochloric acid solution and water, dried over sodium sulfate, and evaporated to dryness to yield N-( l-chlorophenyl)-2,2,4-trichlorobutyramide as a solid which was combined with the crop obtained by filtration and used as such in the next step.

(B) 3,3-dichloro-1- (4-chlorophenyl) -2-pyrrolidinone To a stirred solution of the N-(4-chlorophenyl)-2,2,4- trichlorobutyramide, from Example 1A, in 200 ml. ethyl alcohol was added a solution of 4.2 g. sodium hydroxide in 42 ml. water. Stirring was continued for ten minutes and dilute aqueous hydrochloric acid solution was added until the solution turned acidic, followed by 300 ml. water. The resulting crystals were filtered to give after recrystallization from carbon tetrachloride 18.4 g. 3,3- dichloro-1-(4 chlorophenyl) 2-pyrrolidinone; M.P. 108.4109.2 C. (corn).

METHOD 2 (A) N-(4-chlorophenyl)-4-chlorobutyramide To a stirred, ice cooled mixture of 25.5 g. of 4-chloroaniline and 25.3 g. triethylamine in 800 ml. dry methylene dichloride was added a solution of 31 g. 4-chlorobutyryl chloride in 300 ml. dry methylene dichloride drop- Wise during one hour. The resulting solution was allowed to warm to room temperature, washed with 5% aqueous sodium carbonate solution and water, dried over anhydrous calcium sulfate and evaporated to dryness under reduced pressure to give after successive recrystallizations from ethyl acetate-hexane and ethyl alcohol-hexane 17.9 g. N-( t-chlorophenyl)-4-chlorobutyramide; M.P. 100-101 C.

(B) 1-(4-chlorophenyl)-2-pyrrolidinone To a stirred solution of 11.6 g. N-(4-chlorophenyl)-4 chlorobutyramide in ml. ethyl alcohol was added 5 ml. of a solution of 0.5 g. sodium hydroxide in water and three additional identical sodium hydroxide solutions were added at ten, twenty and forty minute intervals. The solution was allowed to stand for fifteen hours, diluted with 25 ml. water and the resulting crystals were collected by filtration to give after recrystallization from ethyl alcohol-hexane 5.9 g. 1-(4-chlorophenyl)2-pyrrolidinone; M.P. 96.597.5 C.

(C) 3 ,3-dicl1loro-1-(4-chlorophenyl)-2-pyrrolidinone To a stirred slurry of 15.6 phosphorus pentachloride in 65 ml. xylene was added a solution of 4.9 g. 1-(4- chlorophenyl)-2-pyrrolidinone in 40 ml. xylene dropwise during five minutes and the resulting mixture was slowly heated to C. during twenty minutes and heating at 80 C. was continued for forty-five minutes. The solvent was removed under reduced pressure at about 75 C. and the residual viscous oil was stirred with 55 ml. 10% aqueous sodium carbonate and ice. The resulting solid was collected by filtration and washed with Water to give after recrystallization from methyl alcohol-water 3.9 g. 3,3-dichloro-1-(4-chlorophenyl)-2-pyrrolidinone; M.P. 112-113 C.

EXAMPLE 2 (A) N- Z-chlorophenyl -2,2,4-trichlorobutyramide To a stirred, ice-cooled mixture of 9.5 g. 2-chloroaniline in ml. ethylene dichloride and 3.15 g. sodium hydroxide in 75 ml. water was added 15.8 g. 2,2,4-trichlorobutyryl chloride in 50 ml. ethylene dichloride during onehalf hour and stirring was continued one-half hour. The ethylene dichloride phase was separated, washed with dilute aqueous hydrochloric acid and water and evaporated to dryness to yield N-(Z-chlorophenyl)-2,2,4-trichlorobutyramide as a yellow oil which was used as such in the next step.

(B) 3,3-dichlorol 2-chlorophenyl -2-pyrrolidinone To a stirred solution of the N-(2-chlorophenyl)-2,2,4- trichlorobutyramide from Example 2A in ml. ethyl alcohol was added a solution of 3.15 g. sodium hydroxide in 32 ml. water in small portions during one-half hour and stirring was continued for one-half hour. On standing a precipitate formed which was collected by filtration and recrystallized from benzene-hexane to yield 6.9 g. 3,3- dichloro-l-(Z chlorophenyl)-2-pyrrolidinone; M.P. 91- 92 C.

Following a procedure similar to that described in Example 2A and substituting for 2-chloroaniline an equivalent amount of:

(b) N-(2-bromo-4,6-dinitrophenyl)-2,2,4-trichlorobutyramide (c) N- 3,4-diethoxyphenyl) -2,2,4-trichlorobutyramide (d) N-(4-butylmercaptophenyl)-2,2,4-trichlorobutyramide (e) N-(2,4,5-trichlorophenyl)-2,2,4-trichlorobutyramide (f) N-(2-bromo-6-chloro-4-nitrophenyl)-2,2,4-trichlorobutyramide (g) N- [4- (5-phenylpentyloxy) phenyl] -2,2,4-trichlorobutyramide (h) N- (4-phenethyloxyphenyl)-2,2,4-trich1orobutyramide (i) N-(2-bromo-4-isopentylphenyl)-2,2,4-trichlorobutyramide (j) -N-(2,5-dimethyl-4-nitrophenyl)-2,2,4-trichlorobutyramide k) N- (Z-butoxyphenyl -2,2,4-trichlorobutyramide (l) N-(2,6-dichloro-4-ethylmercaptophenyl)2,2,4-

trichlorobutyramide (m) N- [4- (tert-butyl) sulfonylphenyl] -2,2,4-trichlorobutyramide (n) N-{4-[3-(4-nitrophenyl)propyl]phenyl}-2,2,4-

trichlorobutyramide (o) N-(4-dimethylaminophenyl)-2,2,4-trichlor0- butyramide (p) N- (4-dibutylaminophenyl -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and substituting for 2,2,4-trichlorobutyryl chloride an equivalent amount of 6-chlorohexanoyl chloride there can be obtained:

N- (2-chlorophenyl) -6-chlorohexanamide Following a procedure similar to that described in Example 2B and substituting for N-(Z-chlorophenyl)-2,2,4- trichlorobutyramide an equivalent amount of:

(a) N- [4- (n-butyl phenyl] -2,2,4-trichlorobutyramide (b) N-(2-bromo-4,6-dinitrophenyl)-2,2,4-trichlorobutyramide (c) N-(3,4-diethoxyphenyl)-2,2,4-trichlorobutyramide (d) N-(4-butylmercaptophenyl)-2,2,4-trichlorobutyramide (e) N-(2,4,5-trichlorophenyl)-2,2,4-trichlorobutyramide (f) N-(2-bromo-6-chloro-4-nitrophenyl)-2,2,4-trichlorobutyramide (g) N- [4-(5-phenylpentyloxy)phenyl]-2,2,4-trichlorobutyramide (h) N-(4-phenethyloxyphenyl)-2,2,4-trichlorobutyramide (i) N-(2-bromo 4-isopentylphenyl)-2,2,4-trichlorobutyramide (j) N- (2,5 -dimethyl-4-nitrophenyl -2,2,4-trichlorobutyramide (k) N-(Z-butoxyphenyl)-2,2,4-trichlorobutyramide (l) N-(2,6-dichloro-4-ethylmercaptophenyl)-2,2,4-

trichlorobutyramide (m) N- [4- (tert-butyl sulfonylphenyl] 2,2,4-trichlorobutyramide (n) N-{4- [3- (4-nitrophenyl) propyl] phenyl}2,2,4-trichlorobutyramide (o) N-(4-dimethylaminophenyl)-2,2,4-trich1orobutyramide (p) N-(4-dibutylaminophenyl)-2,2,4-trichlorobutyramide (q) N-(2-chlorophenyl)- 6-chlorohexanamide there can be obtained respectively, according to this invention:

(a) 3,3-dichloro-l-[4-(n-butyl)phenyl]-2-pyrrolidinone (b) 3,3-dichloro-1-(2-bromo-4,6-dinitrophenyl)-2- pyrrolidinone (c) 3,3-dichloro-1-(3,4-diethoxyphenyl)-2-pyrrolidinone (d) 3,3-dichloro-1-(4-butylmercaptophenyl)-2- pyrrolidinone (e) 3,3-dichloro-1-(2,4,5-trichlorophenyl)-2- pyrrolidinone (f) 3,3-dichloro-1-(Z-bromo-6-chloro-4-nitrophenyl)- 2-pyrrolidinone (g) 3,3-dichloro- 1- [4- (S-phenylpentyloxy phenyl] 2-pyrro1idinone (h) 3,3-dichloro-1-(4-phenethyloxyphenyl)-2- pyrrolidinone (i) 3,3-dichloro-1-(2-bromo-4-isopentylphenyl)-2- pyrrolidinone (j) 3,3-dichloro-l-(2,5-dimethyl-4-nitrophenyl)-2- pyrrolidinone (k) 3,3-dichloro-1-(2-butoxyphenyl)-2pyrrolidinone (1) 3,3-dichloro-1-(2,6-dichloro-4-ethylmercaptophenyl)-2-pyrrolidinone (m) 3, 3-dichloro-1- [4- (tert-butyl) sulfonylphenyl)- 2-pyrrolidinone (n) 3,3-dichloro-1-{4-[3-(4-nitrophenyl)propyl]phenyl}-2-pyrro1idinone (o) 3,3-dichloro-1-(4-dimethylaminophenyl)-3-pyrrolidinone (p) 3,3-dichloro-l-(4-dibutylaminophenyl)-2-pyrro1idinone (q) 1-(2-chlorophenyl)-hexahydro-2H-azepin-2-one Following the general procedure described hereinbefore for the chlorination of a 2-oxopolymethylenimine and using the following:

1-(2-chlorophenyl)-hexahydro-ZH-azepin-Z-one there can be obtained:

3,3-dichloro-l-(2-chlorophenyl)-hexahydro-2H-azepin- 2-one Following a procedure similar to that described in Example 2A and substituting for 2-chloroaniline and sodium hydroxide an equivalent amount of 4-acetoxyaniline and triethylarnine respectively and omitting the 75 ml. water, there can be obtained according to this invention N-(4-acetoxyphenyl)- 2,2,4-trichlorobutyramide.

Following a procedure similar to that described in Example 2B and substituting for N-(2-chlorophenyl)-2,2,4- trichlorobutyramide an equivalent amount of N-(4-acetoxyphenyl)-2,2,4-trichlorobutyramide and increasing the amount of ethyl alcohol from ml. to 300 ml., there can be obtained 3,3-dichloro-l-(4-acetoxyphenyl)-2-pyrrolidinone.

By treating 3,3-dichloro-l-(4-aeetoxyphenyl)-2-pyr rolidinone in aqueous methyl alcohol, at room temperature, with an amount of potassium hydroxide which is in slight excess of that required to hydrolyze the acetoxy group, there can be obtained 3,3-dichloro-1-(4-hydroxyphenyl)-2-pyrrolidinone.

EXAMPLE 3 (A) N-(3-chlorophenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 6.37 g. 3-chloraniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(3chlorophenyl)-2,2,4- trichlorobutyramide as an orange oil which was used as such in the next step.

(B) 3,3-dichloro-1-(3-chlorophenyl)-2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(3-chlorophenyl)-2,2,4-trichlorobutyramide from Example 3A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 6.7 g. 3,3-dichloro-1-(3-chloro' phenyl)-2-pyrrolidinone; M.P. 76-775" C.

EXAMPLE 4 (A) N-(3-fluorophenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 5.55 g. .3-fluoroaniline, 2.1 g.

11 sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(3-fiuorophenyl)-2,2,4-trichlorobutyramide as an orange oil which was used as such in the next step.

(B) 3,3-dichlorol- S-fluorophenyl) -2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(3-fluorophenyl)-2,2,4-trichlorobutyramide from Example 4A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from benzene-hexane 9.8 g. 3,3-dichloro-l-(4-brornophenyl)-2- pyrrolidinone; M.P. 88-90 C.

EXAMPLE 5 (A) N- (4-fiuorophenyl -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 5.55 g. 4-fluoroaniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride there was obtained N-(4-fluorophenyl)-2,2,4-trichlorobutyramide as brown crystals which was used as such in the next step.

(B) 3 3-dichlorol- 4-fiuorophenyl -2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-fluorophenyl)-2,2,4-trichlorobutyramide from Example 5A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 5.8 g. 3,3-dichloro-1-(4-fluorophenyl)-2-pyrrolidinone; M.P. 106-107 C EXAMPLE 6 (A) N- (4-bromophenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 8.6 g. 4-bromoaniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-bromophenyl)-2,2,4-trichlorobutyramide as a yellow oil which was used as such in the next step.

(B) 3 ,3-dichloro-1-(4-bromophenyl)-2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-bromophenyl)-2,2,4-trichlorobutyramide from Example 6A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from benzene-hexane 9.8 g. 3,3-dichloro-1-('4-bromophenyl)-2- pyrrolidinone; M.P. 122124 C.

EXAMPLE 7 (A) N-phenyl-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 4.65 g. aniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-phenyl-2,2,4-trichlorobutyramide as a yellow solid which was used as such in the next step.

(B 3 ,3-dichlorol-phenyl-Z-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-phenyl-2,2,4-trichlorobutyramide from Example 7A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 6.3 g. of 3,3-dichloro-l-phenyl-Z-pyrrolidinone; M.P. 85-87 C.

EXAMPLE 8 (A) N-(4-tolyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 5.35 g. p-toluidine, 2.1 g. of sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-tolyl)-2,2,4-trichlorobutyramide as an oil which was used as such in the next step.

l 2 (B) 3 ,3-dichlorol- (4-tolyl -2-pyrrolidinone Following a procedure similar to that described in "Example 2B and using the N (4-tolyl)-2,2,4-trichlorobutyramide from Example 8A and 2.1 g. sodium h'ydroxide, there was obtained after recrystallization from benzene-hexane 7.6 g. 3,3-dichloro-l-(4-tolyl)-2-pyrrolidinone; M.P. 118-1l9.5 C.

EXAMPLE 9 (A) N-(4-methoxyphenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 6.15 g. p-anisidine, 2.1 g. sodium hydroxide and 10.5 g. 2,2,4-trichlorobutyryl chloride, chloride, there was obtained N-(4-methoxyphenyl)-2,2,4- trichlorobutyramide as brown crystals which were used as such in the next step.

(B) 3,3-dichloro-1-(4-methoxyphenyl)-2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-methoxyphenyl)-2,2,4- trichlorobutyramide from Example 9A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from ethyl acetate 5.9 g. 3,3-dichloro-1-(4-methoxyphenyl)- 2-pyrrolidinone; M.P. 121121.5 C.

EXAMPLE 10 (A) N- 3 ,4-dimethoxyphenyl -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 7.2 g. 3,4-dimethoxyaniline, 2.0 g. sodium hydroxide, and 9.9 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(3,4-dimethoxyphenyl)-2,2,4- trichlorobutyramide which was used without further purification in the next step.

(B) 3,3-dichlorol- 3,4-dimethoxyphenyl 2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(3,4-dimethoxyphenyl)-2,2,4- trichlorobutyramide from Example 10A and 2.0 g. sodium hydroxide, there Was obtained after recrystallization from acetone 6.9 g. 3,3 dichloro-1-(3,4-dimethoxyphenyl)-2- pyrrolidinone; M.P. 183l85 C.

EXAMPLE 1 l (A) N- 3-chloro-6-methoxyphenyl -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 7.87 g. 3-chloro-G-methoxyaniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4 trichlorobutyryl chloride, there was obtained N-(3-chloro-6-methoxyphenyl) 2,2,4 trichlorobutyramide as a brown oil which was used as such in the next step.

(B) 3,3-dichloro-1-(3-chloro-6-methoxyphenyl -2- pyrrolidinone (A) N-(4-benzyloxyphenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 10 g. 4-benzyloxyaniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-benzyloxyphenyl) 2,2,4 trichlorobutyramide as a solid which was used as such in the next step.

13 (B) 3,3-dichloro-1-(4-benzyloxyphenyl)-2- pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-benzyloxyphenyl)-2,2,4-trichlorobutyramide from Example 12A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from benzene-hexane 9.5 g. 3,3-dichloro-1-(4-benzyloxyphenyl)-2-pyrrolidinone; M.P. 163.5165 C.

EXAMPLE 13 (A) N-(4-acetamidophenyl)-2,2,4-trich1orobutyramide Following a procedure similar to that described in Example 2A and using 4.5 g. 4-acetamidoaniline, 1.3 g. sodium hydroxide, and 6.3 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-acetamidophenyl)-2,2,4-trichlorobutyramide as a solid which was used as such in the next step.

(B) 3,3-dichloro-1-(4-acetamidophenyl)-2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-acetamidophenyl)-2,2,4-trichlorobutyramide from Example 13A and 1.3 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 4.1 g. 3,3-dichloro-1-(4-acetamidophenyl)- 2-pyrrolidinone; M.P. 195196 C. (dec.).

By treating 3,3 dichloro-1-(4-acetamidophenyl) 2- pyrrolidinone in absolute ethyl alcohol, at room temperature, with an ethereal solution containing an amount of hydrogen chloride slightly in excess of that required to hydrolyze the acetamido group, there can be obtained the hydrochloride salt of 3,3-dichloro-l-(4-aminophenyl)-2-pyrrolidinone which can be converted to the free base by dissolving the salt in ethyl alcohol and treating the resulting solution with an equivalent amount of sodium carbonate in water.

EXAMPLE 14 (A) N-(4-nitr0phenyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 6.9 g. 4-nitroaniline, 4.4 g. sodium bicarbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-nitrophenyl)-2,2,4-trichlorobutyramide as yellow crystals which were used as such in the next step.

(B 3 ,3 -dichloro- 1- 4-nitrophenyl) -2-pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-(4-nitrophenyl)-2,2,4-trichlorobutyramide from Example 14A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from acetone-water 6.0 g. 3,3 dichloro-l-(4-nitrophenyl)-2- pyrrolidinone; M.P. 162163 C.

EXAMPLE 15 (A) [4-(trifiuoromethyl) phenyl]-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 8.05 g. 4-(trifluoromethyl)aniline, 4.4 g. sodium bicarbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N- [4- (trifluoromethyl)phenyl]-2,2,4trichlorobutyramide as yellow crystals which was used as such in the next step.

(B) 3,3-dichloro-1- [4-(trifluoromethyl)phenyl]-2- pyrrolidinone Following a procedure similar to that described in Example 2B and using the N-[4-(trifluoromethyl)phenyl]- 2,2,4-trichlorobutyramide from Example 15A and 2.1 g. sodium hydroxide there was obtained after recrystallization from methyl alcohol 6.4 g. 3,3-dichloro-1-[4-trifluoromethyl)phenyl]-2-pyrrolidinone; M.P. 106107 C.

14 EXAMPLE 16 (A) N- [2- (trifluoromethyl phenyl] -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 2A and using 8.05 g. (2-trifiuoromethyl)aniline, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-[2-(trifluoromethyl)phenyl]-2,2,4-trichlorobutyramide as a yellow oil which was used as such in the next step.

(B) 3,3-dichl0ro- 1- [2-(trifluoromethyl)phenyl]-2- pyrrolidinone A procedure was followed similar to that described in Example 2B, using the N-[2-(trifiuoromethyl)phenyl]- 2,2,4-trichlorobutyramide from Example 16A and 2.1 g. sodium hydroxide, except that the reaction solution was diluted with water and extracted with benzene. Evaporation of the benzene extract to dryness yielded, after recrystallization from hexane, 4.0 g. 3,3-dichloro-l-[2-(trifluoromethyl)phenyl]-2-pyrrolidinone; M.P. 64.5 C.

EXAMPLE 17 (A) N-(2-naphthyl)-2,2,4-trichlorobutyramide To a stirred ice-cooled mixture of 7.16 g. 2-naphthylamine in 150 ml. benzene and 5.63 g. sodium carbonate in water was added 10.5 g. 2,2,4-trichlorobutyryl chloride in 50 ml. benzene during one-half hour and stirring was continued one-half hour with cooling and one and onehalf hours at room temperature. The benzene phase was separated, washed with dilute aqueous hydrochloric acid solution, water, dilute sodium bicarbonate solution and water, dried over calcium sulfate and evaporated to dryness to yield 15.9 g. N-(Z-naphthyl)-2,2,4-trichlorobutyramide as a solid which was used as such in the next step.

B. 3,3-dichloro-1- (Z-naphthyl)-2-pyrro1idinone To the N-(Z-naphthyl)-2,2,4-trichlorobutyramide from Example 17A in ml. ethyl alcohol was added, with stirring, a solution of 1.0 g. sodium hydroxide in 10 ml. Water and when the pH of the reaction mixture retunred to approximately seven an additional solution of 1.0 g. of sodium hydroxide in 10 ml. Water was added. When the pH of the reaction mixture returned to approximately seven, it was adjusted to pH thirteen by the addition of 50% aqueous sodium hydroxide solution and stirring was continued for one hour. The reaction mixture was diluted with water and the resulting precipitate was collected by filtration and recrystallized from methyl alcohol to yield 11.0 g. 3,3-dich1oro-l-(2-naphthyl)-2-pyrrolidinone; M.P. 163.5-164.5 C.

EXAMPLE 18 A. N-(4-chloro-1-naphthyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 17A and using 8.88 g. 4-chloro-l-aminonaphthalene, 5.62 g. sodium carbonate and 10.5 g. 2,2,4-trichloro butyryl chloride, there was obtained 16.6 g. N-(4-chlorol-naphthyl)-2,2,4-trichlorobutyramide which was used as such in the next step.

(B) 3,3-dichloro-1-(4-chltoro-1-naphthyl)-2- pyrrolidinone Following a procedure similar to that described in Example 17B and using 16.6 g. N-(4-chloro-l-naphthyl)- 2,2,4trichlorobutyramide from Example 18A and 1.48 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 11.9 g. 3,3-dichloro-1-(4- chloro-l-naphthyl)-2-pyrrolidinone; M.P. 2119-220 C.

EXAMPLE 19 (A) N-(l-naphthyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 17A and using 7.15 g. l-naphthylamine, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(l-naphthyl) -2,2,4-trichlorobutyramide as a brown gum which was used as such in the next step.

(B) 3,3-dichloro-1-( l-naphthyl)-2-pyrrolidinone Following a procedure similar to that described in Example 17B and using the N-(l-naphthyl)-2,2,4-trichlorobutyramide from Example 19A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 9.05 g. 3,3-dichloro-1-(1-naphthyl)-2-pyrrolidinone; M.P. ISO-151 C.

Following a procedure similar to that described in Ex ample 17A and substituting for Z-naphthylamine an equivalent amount of:

(a) 1-amino-2-bromo-4,7-dinitronaphthalene (b) 1-amino-2-methoxy-6-methylsulfonylnaphthalene (c) l-amino-2-phenethyloxynaphthalene (d) 1-amino-2-phenoxynaphthalene (e) 2-amino-1-methylmercaptonaphthalene (f) 1-amino-5-hexyloxynaphthalene (g) l-amino-3-benzylnaphthalene (h) 1-amino-2- (trifiuoromethyl naphthalene (i) 1-amino-2,4dimethylnaphthalene (j) l-arnino-S-bromonaphthalene (k) 2-amin0-6-tert-butylnaphthalene (l) 2-amino3-bromo-5,6,7,S-tetrahydronaphthalene (In) l-amino4-dimethylaminonaphthalene (n) 2-acetamido-6-aminonaphthalene there can be obtained respectively, according to this invention:

Following a procedure similar to that described in Example 17B and substituting for N-(2-naphthyl)-2,2,4- trichlorobutyramide an equivalent amount of:

(a) N- 2-bromo-4,7-dinitrol-naphthyl -2,2,4-

tr ichlorobutyramide (b) N- (Z-rnethoxy-6-methylsulfonyll-naphthyl -2,2,4-

trichlorobutyrarnide (c) N- (Z-phenethyloxy-1naphthyl) -2,2,4-trichlorobutyramide (d) N- 2-phenoxyl-naphthyl -2,2,4-trichlorobutyramide (e) N-( l-methylmercapto-Z-naphthyl -2,2,4-trichl0robutyramide (f) N- S-hexyloxyl-naphthyl -2,2,4trichlorobutyramide (g) N- (3-benzyl-1-naphthyl)-2,2,4-trichlorobutyramide (h) N-[Z-(trifluoromethyl)-1-naphthyl]-2,2,4-trichlorobutyramide (i) N- (2,4-dimethyl-1-naphthyl)-2,2,4-trichlor0- butyramide (j) N-(S-bromol-naphthyl) -2,2,4-trichlorobutyramide (k) N- 6-tert-butyl-2-naphthyl 2,2,4-trichlorobutyramide (l) N-(3-br0mo-5,6,7,S-tetrahydro-Z-naphthyl -2,2,4-

trichlorobutyramide (m) N- 4-dimethylaminol-naphthyl -2,2,4-trichlorobutyramide (n) N- (2-acetamido-6-naphthyl -2,2,4-trichloro butyramide there can be obtained respectively, according to this invention:

(a) 3,3-dichloro-1-(2-bromo-4,7-dinitro-l-naphthyl)- 2-pyrrolidinone (b) 3,3-dichloro-1-(Z-rnethoxy-S-methylsulfonyl-1- naphthyl)-2-pyrro1idinone c) 3 ,3-dichloro-1- Z-phenethyloxyl-naphthyl -2- pyrrolidinone (d) 3,3-dichloro-1-(2-phenoxy-l-naphthyl)-2- pyrrolidinone (e) 3,3-dichloro1-(1-methylmercapto-Z-naphthyl)-2- pyrrolidinone (f 3,3-dichloro- 1- 5 -hexyl0xyl-naphthyl -2- pyrrolidinone (g) 3,3-dichloro-1-(3-benzyl-l-naphthyl)-2- pyrrolidinone (h) 3,3-dicl1loro-l-[2-(trifiuorornethyl)-1-naphthyl]- 2-pyrrolidinone (i) 3 ,3-dichloro-1-(2,4-dimethyl-1-naphthyl)-2- pyrrolidinone (j 3 ,3-dichloro-1-(8-bromo-1-naphthyl)-2-pyrrolidin0ne (k) 3 ,3-dichloro-1-(6-tert-butyl-2-naphthyl)-2- pyrrolidinone (l) 3,3-dichl0ro-1-(3-bromo-5,6,7,8-tetrahydro-2- naphthyl)-2-pyrrolidinone (m) 3,3-dichloro-1-(4-dimethylamino-l-naphthyl)-2- pyrrolidinone (n) 3,3-dichloro-1-(2-acetamido-6-naphthyl)-2- pyrrolidinone EXAMPLE 20 (A) N(2,6-xylyl)-2,2,4-trichlorobutyran1ide To a stirred ice-cooled mixture of 6.06 g. 2,6-dimethylaniline in ml. benzene and 5.62 g. sodium carbonate in 50 ml. water was added 10.5 g. 2,2,4-trichlorobutyryl chloride in 50 ml. benzene during one-half hour and stirring was continued one-half hour with cooling and one and one-half hours at room temperature. The benzene phase was separated, washed with dilute aqueous hydrochloric acid solution, water, dilute sodium bicarbonate solution and water, dried over calcium sulfate and evaporated to dryness to yield after recrystallization from hexane 12.8 g. N-(2,6-xylyl)-2,2,4-trichlorobutyramide; M.P. 119.0-.0 C.

(B) 3,3-dichloro-1-(2,6-xylyl) -2-pyrrolidinone To 128 g. N-(2,6-xylyl) 2,2,4- trichlorobutyramide from Example 20A in 100 ml. ethyl alcohol was added, with stirring, a solution of 0.8 g. sodium hydroxide in 10 ml. water and when the pH of the reaction mixture returned to approximately seven an additional 0.8 g. sodium hydroxide in 10 ml. water was added. When the pH of the reaction mixture returned to approximately seven, it was adjusted to pH thirteen by the addition of 50% aqueous sodium hydroxide solution and stirring was continued for one hour. The reaction mixture was diluted with water and the resulting precipitate was collected by filtration and recrystallized from methyl alcohol-water to yield 8.7 g. 3,3-dichloro-1-(2,6-xylyl)-2-pyrrolidinone; Ml. 96.598.0 C.

17 EXAMPLE 21 (A) N-(2,4-difluorop henyl)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 20A and using 6.46 g. 2,4-difiuoroaniline, 5.62 g. sodium carbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained 13.16 g. N- (2,-4-difluorophenyl)-2,2,4-tric-hlorobutyramide as an oil which was used as such in the next step.

(B) 3 ,3-dichloro-1-(2,4-difluorophenyl) -2-pyrrolidinone Following a procedure similar to that described in Example 20B and using 13.6 g. N-(2,4-difluorophenyl)- 2,2,4-trichlorobutyramide from Example 21A and 1.80 g. sodium hydroxide, there was obtained after recrystallization from ethyl acetate-hexane 6.43 g. 3,3-dichloro- 1-(2,4-difluorophenyl)-2-pyrrolidinone; M.P. 86-87" C.

EXAMPLE 22 (A) N- 3- (phenoxy phenyl] -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 20A and using 9.26 g. 3-phenoxyaniline, 5.62 g. sodium carbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained 16.4 g. N-[3-(phenoxy) phenyl]-2,2,4-trichlorobiutyramide as an oil which was used as such in the next step.

(B) 3,3-dichloro-1- [3-(phenoxy) phenyl] -2-pyrrolidinone Following a procedure similar to that described in Example 203 and using 16.4 g. N-[3-(phenoxy)phenyl]- 2,2,4-trichlorobutyramide from Example 22A and 3.83 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 12.2 g. 3,3-dichloro-1- [3 (phenoxy)phenyl] 2 pyrrolidinone; M.P. 89.5- 90.5 C.

EXAMPLE 23 (A) N [4-chloro-2- (trirfluoromethyl phenyl] -2,2,4- trichlorobutyramide Following a procedure similar to that described in Example 20A and using 9.78 g. 4-chloro-2-(trifluoromethy1)-aniline, 5,62 g. sodium carbonate, and 10.5 g. 2,2,4-trichlorobutyrylchloride there was obtained N-[4- ch1oro-2-(trifluoromethyl)phenyl] 2,2,4 trichlorobutyramide as crystals which were used as such in the next step.

('B) 3, 3 -dichloro-1-[44ch1oro-2-(trifiuoromethyl)phenyl] 2-pyrrolidinone Following a procedure similar to that described in Example 20B and using the N-[4-chloro-2-(trifiuoromethyl)phenyl]-2,2,4trichlorobutyramide from Example 23A and 2.0 g. sodium hydroxide, there was obtained after recrystallization from'hexane 7.97 g. 3,3-dichloro-1-[4- chloro-2-(trifluoromethyl)phenyl]-Z-pyrrolidnone; M.P. 7880 C.

EXAMPLE 24 (A) N-[3,5-bis(trifluoromethyl)phenyl]-2,2,4- trichlorobutyramide Following a procedure similar to that described in Example 20A and using 11.5 g. 3,5-bis(trichloromethyl) aniline, 5.62 g. sodium carbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained 19.9 g. N-[3,5- bis (trifluoromethyl) phenyl] -2,2,4-trichlorobutyramide as a solid which was used as such in the next step.

(B 3 ,3 -dichloro-1-[3 ,5 -bis(trifluoromethyl)phenyl] 2-pyrrolidinone Following a procedure similar to that described in Example 20B and using the N-[3,5-bis(trifluoromethyl) phenyl] 2,2,4- trichlorobutyramide from Example 24A and 1.98 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 8.19 g. 3,3- dichloro-l-[3,5-bis(trirfi1uoron1ethyl) phenyl] 2 pyrrolidinone; M.P. 88-90 C.

18 EXAMPLE 25 (A) N-(2,6-dimethyl-3-pyridyl)-2,2,4- trichlorobutyramide To a stirred, ice-cooled mixture of 6.1 g. 3-amino-2,6- dimethylpyridine in ml. ethylene dichloride and 4.2 g. sodium bicarbonate in 50 ml. water was added 10.5 g. 2,2,4-trichlorobutyrylchloride in 25 ml. ethylene dichloride during one-half hour and stirring was continued onehalf hour. The ethylene dichloride phase was washed with dilute aqueous sodium bicarbonate solution and water and the ethylene dichloride layer was then extracted with one normal aqueous hydrochloric acid solution and water. The aqueous acidic solution was treated with aqueous sodium bicarbonate solution until neutral and the resulting oily precipitate was taken up in ether and the ethereal solution was dried over calcium sulfate and evaporated to dryness. The resulting oil, dissolved in acetone, was treated with one equivalent of hydrogen chloride in ethyl alcohol to yield after recrystallization from ethyl alcohol-acetone 8.1 g. of the hydrochloride of N-(2,6 dimethyl-3-pyridyl)-2,2,4-trichlorobutyramide; M.P. 181 C. (dcc.).

B. 3,3-dichloro-1-(2,6-dimethyl-3-pyridyl)-2-pyrrolidinone To a stirred solution of 5 g. of the hydrochloride of N (2,6 dimethyl-3-pyridyl)-2,2,4-trichlorobutyramide from Example 25A in 30 ml. ethyl alcohol was added a solution of 1.2 g. sodium hydroxide in 12 ml. water in small portions during twenty minutes and stirring was continued for one-half hour. The reaction solution was diluted with water and the resulting precipitate was collected by filtration and recrystallized from methyl-alcoholwater to yield 1.12 g. 3,3-dichloro-l-(2,6-dimethyl-3-pyridyl)-2-pyrrolidinone; M.P. 87.8-89.8 C. (corr.).

EXAMPLE 26 A. N-(2-chloro-3-pyridyl)-2,2,4-trichlorobutyramide A procedure was followed similar to that described in Example 25A using benzene instead of ethylene dichloride, 6.43 g. 3-amino-2-chloropyridine, 5.62 g. sodium carbonate, and 10.5 g. 2,2,4-trich1orobutyryl chloride, except that the benzene phase was washed only with water and then evaporated to dryness to yield 14.8 g. N-(2-ch1oro-3- pyridyl)-2,2,4-trichlorobutyramide as crystals which were used as such in the next step.

B. 3,3-dichloro-1-(2-chloro-3-pyridyl)-2-pyrrolidinone Following a procedure similar to that described in Ex ample 25B and using 14.8 g. N-(2-chloro-3-pyridyl)-2,2,4- trichlorobutyra'mide from Example 26A and 1.96 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 8.1 g. 3,3-dichloro-1-(2-chloro-3- pyridyl)-2-pyrrolidinone; M.P. 128130 C.

Following a procedure similar to that described in Example 25A and substituting for 3-amino-2,6-dimethylpyridine an equivalent amount of:

(a) 2-aminopyridine (b) S-aminopyridine (c) 4-aminopyridine (d) S-amino-Z- dimethylaminopyridine (e) 2-amino-6-hexylpyridine (f) 3-amino-6-ethoxy-2-methylmercaptopyridine (g) 3-arnino-4-phenethylpyridine (h) 5-amino-Z-benzyloxypyridine (i) 4-amino-2,4-dichloro-6-(trichloromethyl)pyridine (j) 5-amino-2-n-butylmercapto-3-nitropyridine (k) 3-amino-5-chloro-2-phenoxypyridine (l) 2-amino-S-tert-butylpyridine (m) 2-amino-3,5,6-trifiuoropyridine (n) 5-amino-2- (n-butyls ulfonyl)pyridine (o) 2-acetamido-6-aminopyridine 19 there can be obtained respectively, according to this invention:

(a) N- 2-pyridyl -2,2,4-trichlorobutyramide (b) N- 3 -pyridy1) -2, 2,4-trichlorobutyramide (c) N- 4-pyridyl -2,2,4-trichlorobutyramide d) N- Z-dimethylamino--pyridyl) -2,2,4-trichlorobutyramide (e) N- 6-hexyl-2-pyridyl) -2,2,4-trichlorobutyramide (f) N- 6-ethoxy-2-methylmercapto-3 -pyridyl -2,2,4-trichlorobutyramide (g) N- 4-phenethyl-3-pyridyl -2,2,4-trichlorobutyramide (h) N- 2-benzyloxy-5 -pyridy1 -2,2,4-trichlorobutyramide (i) N- [2,3-dichloro-6- (trichloromethyl -4-pyridyl] -2,2,4-

trichlorobutyramide (j) N (2-n-butylmercapto-3 -nitro-5 -pyridy1 -2,2,4-trichlorobutyramide (k) N (5-chloro-2-phenoxy-3-pyridyl -2,2,4-trichlorobutyramide (1) N 5 -tert-butyl-2-pyridyl -2,2,4-trichlorobutyramide (m) N- 3,5 ,6-trifluoro-2-pyridyl -2,2,4-trichlorobutyramide (n) N- 2-n-butylsulfonyl-S-pyridyl -2,2,4-trichlorobutyramide (o) N- (2-acetamido-6-pyridyl) -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example B and substituting for N-(2,6-dimethyl-3-pyri dyl)-2,2,4-trichlorobutyramide an equivalent amount of:

(a) N-(2-pyridyl)-2,2,4-trichlorobutyramide (b) N- 3-pyridyl -2,2,4-trichlorobutyramide (c) N-(4-pyridyl)-2,2,4-trichlorobutyramide (d) N-(Z-dimethylamino-S-pyridyl)-2,2,4-tichlorobutyramide (e) N- 6-hexyl-2-pyridy -2,2,4-trichlorobutyramide (f) N-(6-ethoxy-2-methylmercapto-3-pyridyl)-2,2,4-

trichlorobutyramide (g) N-(4-phenethyl-3-pyridyl) -2,2,4-trichlorobutyramide (h) N-(Z-benzyloxy-S-pyridyl)-2,2,4-trichlorobutyramide (i) N- 2,3-dichloro-6- (trichloromethyl -4-pyridyl] -2,2,4--

trichlorobutyramide (j N- 2-n-butylmercapto-3-nitro-5-pyridyl) -2,2,4-trichlorobutyramide k) N- 5 -chloro-2-phenoxy-3 -pyridyl -2,2,4-trichlorobutyramide (l) N- 5-tert-butyl-2-pyridyl -2,2,4-trichlorobutyramide (m) N-(3,5,6-trifluoro-2-pyridyl)-2,2,4-trichlorobutyramide (n) N-(2-n-butylsulfonyl-5-pyridy1)-2,2,4-trichlorobutyramide (o) N-(2-acetamido-6-pyridyl)-2,2,4-trichlorobutyramide there can be obtained respectively, according to this invention:

(a) 3,3-dichloro-1-(2-pyridyl)-2-pyrrolidinone (b) 3,3-dichlorol- 3-pyridyl -2-pyrrolidinone (c) 3,3-dichloro-1-(4pyridyl) -2-pyrrolidinone (d) 3 ,3-dichloro-1-(Z-dimethylamino-5-pyridyl) -2- pyrrolidinone (e) 3,3-dichlorol- 6-hexyl-2-pyridyl -2-pyrrolidinone (f 3 ,3-dichloro-1- (6-ethoxy-Z-methylmercapto-3-pyridyl) -2-pyrrolidinone (g) 3,3-dichloro-1-(4-phenethyl) -3-pyridyl) -2-pyrrolidinone (h) 3,3-dichloro-1- (Z-benzyloxy-S-pyridyl) -2-pyrrolidinone (i) 3,3-dichloro-1-[2,3-dichloro-6-(trich1oromethyl)-4- pyridyl -2-pyrrolidinone (j) 3,3 -dichlorol- (2-n-butylmercapto-3-nitro-5-pyridyl) 2-pyrrolidinone 20 (k) 3 ,3-dichloro-1-(5-chloro-2-phenoxy-3-pyridyl)-2- pyrrolidinone (l) 3,3-dichlorol- ('5-tert-butyl-2-pyridyl -2-pyrro1idinone (In) 3 ,3-dichloro- 1 3,5 ,6-trifluoro-2-pyridyl) 2-pyrrolidinone (n) 3,3-dichlorol- (Z-n-butylsulfonyl-5-pyridyl -2- pyrrolidinone o) 3,3-dichloro- 1- 2-acetamido-6-pyridyl -2-pyrrolidinone By treating 3,3-dichloro-1-(2-acetamido-6-pyridyl)-2- pyrrolidinone in absolute ethyl alcohol, at room temperature, with an ethereal solution containing an amount of hydrogen chloride slightly in excess of that required to hydrolyze the acetamido group, there can be obtained the dihydrochloride salt of 3,3-dichloro-1-(2-amino-6-pyridyl)-2-pyrrolidinone which can be converted to the free base by dissolving the salt in ethyl alcohol and treating the resulting solution with an equivalent of sodium carbonate in water.

EXAMPLE 27 (A) N-(5-chloro-2-pyridyl) -2,2,4-trichlorobutyramide Following a procedure similar to that described for Example 25A and using 11.9 g. 2-amino-5-chloropyridine, 6.42 g. sodium carbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained 11.9 g. N-(5-chloro-2- pyridyl)-2,2,4-trich1orobutyramide as crystals which was used as such in the next step.

(B) 3,3-dichloro-l-(5chloro-2-pyridyl)-2-pyrrolidinone Following a procedure similar to that described in Example 25B and using 11.9 g. N-(5-chloro-2-pyridyl)-2,2,4- trichlorobutyramide from Example 27A and 1.58 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 3.56 g. 3,3-dichloro 1-(5-chloro- Z-pyridyl)-2-pyrrolidinone; M.P. l0'6107 C.

EXAMPLE 28 (A) N- (4-chloro-2-benzothiazolyl)-2,2,4-trichlorobutyramide To a stirred ice-cooled mixture of 9.2 g. 2-amino-4- chlorobenzothiazole in 700 ml. ethylene dichloride and 5.63 g. sodium carbonate in ml. water was added a solution of 10.5 g. 2,2,4-trichlorobutyryl chloride in 50 ml. ethylene dichloride dropwise during twenty minutes. Stirring was continued for two hours at room temperature and the ethylene dichloride phase was separated and washed with water, dried over sodium sulfate and evaporated to dryness to yield, after recrystallization from methyl alcohol-acetone-water, 13.6 g. N-(4-chloro-2-benzothiazolyl)-2,2,4-trichlorobutylramide; M.P. -155 C.

(B) 3,3-dichloro-1- (4-chloro-2-benzothiazolyl) 2-pyrrolidinone To a stirred solution of 13.6 g. N-(4-chloro-2-benzothiazolyl)-2,2,4-trichlorobutyramide from Example 28A in 400 ml. methyl alcohol at room temperature was added a solution of 1.53 g. sodium hydroxide in 10 ml. water dropwise. The pH of the mixture was adjusted to seven by the addition of a few drops 1 N aqueous hydrochloric acid solution and stirring was continued for five minutes. The mixture was diluted with 30 ml. water and the precipitate was collected by filtration and recrystallized from benzene-methyl alcohol to yield 9.36 g. 3,3-dichloro-l-(4-chloro 2 benzothiazolyl)-2-pyrrolidinone; M.P. 208-209 C.

Following a procedure similar to that described in Example 28A and substituting for 2-amino-4-chlorobenzothiazole an equivalent amount of:

(a) Z-aminobenzothiazole (b) 4-aminobenzothiazole (c) S-aminobenzothiazole (d) 6-aminobenzothiazole (e) 7-aminobenzothiazole 21 (f) 2-amino-6-n-butoxybenzothiazole (g) 2-amin0-5,7-dichloro-4-methoxybenzothiazole (h) 2-amino-6-ethylmercaptobenzothiazole (i) '6-amino-2-phenoxybenzothiazole (j) 6-amino-Z-dimethylaminobenzothiazole (k) 2-amin0-6- (trifluoromethyl)benzothiazole (l) 2-amino-4-bromo-6-methylsulfonylbenzothiazole (m) 5-amino-2-methyl-4-nitrobenzothiazole (n) Z-acetamido-6-aminobenzothaizole there can be obtained respectively, according to this invention:

(a) N- 2-benzothiazolyl -2,2,4-trichlorobutyramide (b) N- (4-benzothiazolyl)-2,2,4-trichlorobutyramide (c) N-(S-benzothiazolyl)-2,2,4-trichlorobutyramide (d) N-(6-benzothiazolyl)-2,2,4-trichlorobutyramide (e) N- 7 -benzothiazolyl -2,2,4-trichlorobutyramide (f) N-(6-n-butoxy-2-benzothiazolyl)-2,2,4-trichlorobutyramide (g) N- 5 ,7-dichloro-4-methoxy-2-benzothiazolyl 2,2,4-trichlorobutyramide (h) 6-(N-ethylmercapto-2-benzothiazolyl)-2,2,4-

trichlorobutyramide (i) N-(2-phenoxy-6-benzothiaz0lyl)-2,2,4-trichlor0- butyramide (1 N-( Z-dimethylamino-6-benzothiazolyl -2,2,4-trichlorobutyramide (k) N- 6- (trifluoromethyl) -2-benzothiaz0lyl] -2,2,4-

trichlorobuytramide (l) N-(4-bromo-6-mcthylsulfonyl-2-benzothiazolyl)- 2,2,4-trichlorobutyramide (m) N- 2-methyl-4-nitro-5-benzothiazolyl) -2,2,4-

trichlorobutyramide (n) 2-acetamido-6-aminobenzothiazole butyramide Following a procedure similar to that described in Example 28-B and substituting for N-(4-chloro-2-benzothiazolyl)-2,2,4-trichlorobutyramide an equivalent amount of:

there can be obtained respectively, according to this invention:

(a) 3,3-dichloro-l-(2-benzothiazolyl)-2-pyrrolidinone (b) 3,3dichloro-1-(4-benzothiazolyl)-2-pyrrolidinone (c) 3,3-dichloro-1-(S-benzothiazolyl)-2-pyrrolidinone (d) 3,3-dichloro-1- (6-benzothiazolyl) -2-pyrrolidinone (e) 3,3-dichloro-1-(7-benzothiazolyl)-2-pyrrolidinone (f) 3,3-dichloro-1-(6-n-butoxy-2-benzothiazolyl)- 2-pyrrolidin0ne (g) 3,3-dichloro-l-(5,7-dichloro-4-methoxy-2- benzothiazolyl -2-pyrrolidinone (h) 3 ,3-dichloro-1-(6-ethylmercapto-2-benzothiazolyl)-2-pyrrolidinone (i) 3,3-dichloro-1-(2-phenoxy-6-benzothiazolyl)-2-pyrrolidinone (j) 3 ,3-dichloro-1-(Z-dimethylamino-6-benzothiazolyl)- 2-pyrrolidinone (k) 3 ,3-dichlorol- 6- (trifluoromethyl) -2-benzothiazolyl] -2-pyrrolidinone (l) 3,3-dichloro-1-(4-bromo-6-methylsulfonyl-2- benzothiazolyl -2-pyrrolidinone (m) 3 ,3-dichloro-1-(2-methyl-4-nitro-5-benzothiazolyl)- 2-pyrrolidinone (n) 3 ,3-dichloro-1-(2-acetamido-6-benzothiazolyl)- 2-pyrrolidinone By treating 3,3-dichloro 1 (2-acetamido-6-benzothiazolyl) 2 pyrrolidinone in absolute ethyl alcohol,

at room temperature, with an etheral solution containing an amount of hydrogen chloride slightly in excess of that required to hydrolyze the acetamido group, there can be obtained the hydrochloride salt of 3,3-dichloro-1- (2 amino 6 benzothiazolyl) 2 pyrrolidinone which can be converted to the free base by dissolving the salt in ethyl alcohol and treating the resulting solution with an equivalent amount of sodium carbonate in water.

EXAMPLE 29 (A) N- (9-oxo-l-fiuorenyl)-2,2,4-trichlorobutyramide To a stirred mixture of 5.65 g. l-amino-9-fluorenone in 500 ml. ethylene dichloride and 3.83 g. sodium carbonate in ml. water, at room temperature, was added a solution of 6.12 g. 2,2,4-trichlorobutyryl chloride in 50 ml. ethylene dichloride dropwise during twenty minutes. Stirring Was continued for sixteen hours and the ethylene dichloride phase was separated and washed with water, dried over sodium sulfate, and evaporated to dryness to yield 10.5 g. N-(9-oxo-l-fluorenyl)-2,2,4-trichlorobutyramide; M.P. l43l45 C.

(B) 3,3-dichloro-1-(9-oxo-1-fiuorenyl)-2- pyrrolidinone To a stirred solution of 9.5 g. N-(9-oxo l fluorenyl)- 2,2,4-trichlorobutyramide from Example 29A in 300 ml. methyl alcohol-methylene dichloride (prepared by dissolving the amide in ml. refluxing methylene dichloride, adding 200 ml. methyl alcohol, and concentrating the resulting solution to 300 ml.), at room temperature, was added a solution of 1.0 g. sodium hydroxide in 5 ml. water dropwise during five minutes. The reaction mixture was concentrated by evaporation to remove the methylene dichloride and diluted with water to yield after recrystallization from methylene dichloride-methanol 6.8 g. 3,3 dichloro 1 (9 oxo 1 fluorenyl) 2 pyrrolidinone; M.P. -161 C.

Following a procedure similar to that described in Example 29A and substituting for 1-amino-9-fluorenone an equivalent amount of:

(a) l-aminofiuorene (b) 2-aminofiu0rene (c) 3-aminofluorene (d) 4-aminofluorene (e) 3-amino-2-dimethylaminofluoren-9-one (f) 2-amino-l,3-dibromo-7-nitrofluorene (g) 2-amino-7-methylsulfonylfiuorene (h) l-amino-Z-methoxyfiuorene (i) 7-a1nino-3-methyl-2-nitrofiuoren-9-one (j) 2-amino-3-bromo-6,7-dichlorofiuoren-9-one (k) 2-amino-7-benzylfiuorene (l) Z-acetamido-3-aminofluorene there can be obtained respectively, according to this invention:

(a) N- l-fiuorenyl -2,2,4-trich1orobutyramide (b) N-(2-fluoreny1)-2,2,4-trichlorobutyramide (c) N- 3-fiuorenyl -2,2,4-trichlorobutyramide (d) N- (4-fiuorenyl -2,2,4-trichlorobutyramide (e) N- 2-diethylamino-9-oxo-3-fiuorenyl -2,2,4-trichlorobutyramide (f) N-( 1,3-dibromo-7-nitro-2-fluorenyl) -2,2,4-trichlorobutyramide (g) N- (7-methylsulfonyl-Z-fluorenyl -2,2,4-trichlorobutyramide (h) N- (Z-methoxyl-fiuorenyl -2,2,4-trichlorobutyramide (i) N- 3-methyl-2-nitro-9-oxo-7-fiuorenyl -2,2,4-

trichlorobutyramide (j) N- 3-bromo-6,7-dichloro-9-oxo-2-fluorenyl -2,2,4-

trichlorobutyramide (k) N- 7-benzyl-2-fluorenyl -2,2,4-trichlorobutyramide (l) N 2-acetamido-3-fiuorenyl -2,2,4-trichlorobutyramide (A) N- (S,6,7,8-tetrahydrol -naphthyl -2,2,4- trichlorobutyramide To a stirred ice-cooled solution of 7.35 g. 5,6,7,8-tetrahydrol-naphthylamine in 250 ml. methylene dichloride and 5.6 g. triethylamine was added 11.6 g. 2,2,4-trichlorobutyryl chloride in 40 ml. methylene dichloride dropwise during fifteen minutes. The mixture was diluted with chloroform and washed with dilute aqueous sodium bicarbonate solution and water. The organic phase was separated, dried over sodium sulfate and evaporated to dryness to yield 17.0 g. N (5,6,7,8 tetrahydro lnaphthyl) 2,2,4 trichlorobutyramide as a yellow oil which was used as such in the next step.

(B) 3,3-dichloro-1- (5,6,7,8-tetrahydr-l-naphthyl)-2- pyrrolidinone To a stirred ice-cooled solution of 16.0 g. N-(5,6,7,8- tetrahydro-l-naphthyl)-2,2,4 trichlorobutyrarnide from Example 30A in 150 ml. methyl alcohol was added a solution of 2 g. sodium hydroxide in 10 ml. water dropwise during five minutes. The reaction mixture was diluted with water and the precipitate was collected by filtration to yield after recrystallization from methylene dichloridehexane 9.2 g. 3,3 dichloro 1 (5,6,7,8-tetrahydro-1- naphthyl)-2-pyrrolidinone; M.P. 12913l C.

EXAMPLE 31 (A) N-(3,4-dichlorobenzyl)-2,24-trichlorobutyrarnide To a stirred ice-cooled mixture of 17.6 g. 3,4-dichlorobenzylamine in 200 ml. ethylene dichloride and 4.2 g. sodium hydroxide in 100 ml. water was added 21 g. 2,2,4-

trichlorobutyryl chloride. The mixture was stirred for one-half hour and the precipitate was filtered and washed with water. The ethylene dichloride layer was washed with dilute hydrochloric acid and water, dried over sodium sulfate, and evaporated to dryness to yield N-(3,4-dichlorobenzyl)-2,2,4-trichlorobutyramide as a solid which was combined with the crop obtained by filtration and used as such in the next step.

(B) 3,3-dichloro-l-(3,4-dichlorobenzyl)-2-pyrrolidinone To a stirred solution of the N (3,4-dichlorobenzyl)- 2.2,4-trichlorobutyramide, from Example 31A, in 200 ml. ethyl alcohol was added a solution of 4.2 sodium hydroxide in 42 ml. water. Stirring was continued for ten minutes and dilute aqueous hydrochloric acid was added until the solution turned acidic, followed by 300 ml. water. The resulting crystals were filtered to give, after recrystallization from chloroformhexane 16.0 g. 3,3-dichloro-l-(3,4- dichlorobenzyl) 2 pyrrolidinone; M.P. 94.094.8 C. (corn).

EXAMPLE 32 (A) N- (4-chlorobenzyl -2,2,4-trichlorobutyramide To a stirred ice-cooled mixture of 7.08 g. 4-chlorobenzylamine in 75 ml. ethylene dichloride and 4.4 g. sodium bicarbonate in 50 ml. water, in a nitrogen atmosphere, was added a solution of 2,2,4-trichlorobutyryl chloride in 25 ml. ethylene dichloride dropwise during onehalf hour and stirring was continued one-half hour. The ethylene dichloride phase was separated, washed with dilute hydrochloric acid and water, and evaporated to dryness to yield N-(4-chlorobenzyl)-2,2,4-trichlorobutyramide which was used as such in the next step.

(B) 3,3-dichloro-1-(4-chlorobenzyl)-2-pyrrolidinone To a stirred solution of the N-(4-chlorobenzyl)-2,2,4- trichlorobutyramide from Example 32A in ml. ethyl alcohol, in a nitrogen atmosphere, was added a solution of 2.1 g. sodium hydroxide in water dropwise during onehalf hour and stirring was continued one-half hour. The precipitate was filtered to give, after recrystallization from methyl alcohol-water 8.2 g. 3,3-dichloro-1-(4-chlor0benzyl)-2-pyrrolidinone, M.P. 7274 C.

Following a procedure similar to that described in Example 32A and substituting for 4-chlorobenzylamine an equivalent amount of (a) S-phenylhexylamine (b) -phenylhexylamine (c) 3- (3 ,4-dichlorophenyl propylamine (d) benzylamine (e) 4-benzylbenzylamine (f) 4-benzyloxybenzylamine- (g) 4-n-butoxy-a-methylbenzylamine (h) 2-chloro-3-methoxy-6-methylbenzylamine (i) 2-chloro-4-metl1ylsulfonylbenzylamine (j) 2-chloro- 6-nitrobenzylamine (k) ot-methyl-4-phenoxybenzylamine (1) 3,4,S-trimethoxybenzylamine (m) 2-methylmercaptobenzylamine (n) 3-(trifluoromethyl)benzylamine (o) 4-dimethylaminophenethylamine there can be obtained respectively, according to this invention:

(a) N-(S-phenylhexyl)-2,2,4-trichlorobutyramide (b) N- 6-phenylhexyl) -2,2,4-trichlorobutyramide (c) N- 3- (3 ,4-dicl1lorophenyl propyl] -2,2,4-trichlorobutyramide (d) N-benzyl-2,2,4trichlorobutyramide (e) N-(4-benzylbenzyl)-2,2,4-trichlorobutyramide (f) N- (4-benzyloxybenzyl -2,2,4-trichlorobutyramide g) N- (4-n-butoxy-ot-methylbenzyl -2,2,4-trichlorobutyramide (h) N- 2-chloro-3-methoxy-6-methylbenzyl) -2,2,4-tri chlorobutyramide (i) N-(2-chloro-4-methylsulfonylbenzyl)-2,2,4-trichlorobutyramide (j) N- (2-chloro-6-nitrobenzyl -2,2,4-trichlorobutyramide (k) N-(a-methyl-4-phenoxybenzyl)-2,2,4-trichlorobutyramide (l) N-(3,4,5-trimethoxybenzyl)-2,2,4-trichlorobutyramide (m) N-(Z-methylmercaptobenzyl)-2,2,4-trichlorobutyramide (n) N- [3- (trifluoromethyl) benzyl] -2,2,4-trichlorobutyramide (o) N- (4-dimethylaminophenethyl) -2,2,4-trichlorobutyramide Following a procedure similar to that described in EX- ample 32B and substituting for N-(4-chlorobenzyl)-2,2,4 trichlorobutyramide an equivalent amount of:

there can be obtained respectively, according to this invention:

(a) 3 ,3-dichloro- 1- S-phenylhexyl -2-pyrrolidinone (b) 3,3-dichloro-1- (6-phenylhexyl) -2-pyrrolidinone (c) 3,3-dichloro-1-[3-(3,4-dichlorophenyl)propyl]-2- pyrrolidinone (d) 3,3-dichloro-l-benzyl-Z-pyrrolidinone e) 3,3-dichloro-1-(4-benzylbenzyl -2-pyrrolidinone (f) 3,3-dichloro-1-(4-benzyloxybenzyl)-2 -pyrrolidinone (g) 3,3-dichloro-1- (4-n-butoxy-a-methylbenzyl) -2- pyrrolidinone (h) 3,3-dichloro-1-(2-chloro-3-methoxy-6-methylbenzyl)- 2-pyrrolidinone (i) 3,3-dichloro-1-(2-chloro-4-methylsulfonylbenzyl)-2 pyrrolidinone (j) 3,3-dichloro-1- (2-chloro-6-nitrobenzyl)-2- pyrrolidinone (k) 3,3-dichloro-1- (ot-methyl-4-phenoxybenzyl) -2- pyrrolidinone (l) 3,3-dichloro-1-(3,4,5-trimethoxybenzyl)-2- pyrrolidinone (m) 3,3-dichloro-1-(Z-methylmercaptobenzyl)-2- pyrrolidinone (n) 3,3-dichloro-1-[3-(trifluoromethyl)benzyl]-2- pyrrolidinone (o) 3 ,3-dichloro-1-(4-dimethylaminophenethyl) -2- pyrrolidinone v 26 EXAMPLE 33 (A) N-(4-chlorophenethy1)-2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 32A and using 7.78 g. 2-(4-chlorophenyl)ethylamine, 4.4 g. sodium bicarbonate, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-(4-chlorophenethyl)-2,2,4-trichlorobutyramide which was used as such in the next step.

(B) 3 ,3-dichlorol- (4-chlorophenethyl -2-pyrrolidinone Following a procedure similar to that described in EX- ample 32B and using the N-(4-chlorophenethyl)-2,2,4- trichlorobutyramide from Example 33A, there was obtained after recrystallization from methyl alcohol 6.3 g. 3,3 dichloro 1 (4 chlorophenethyl)-2-pyrrolidinone; M.P. 7880 C.

EXAMPLE 34 (A) N-phenethyl-Z,2,4-trichl0robutyramide Following a procedure similar to that described in Example 32A and using 6.05 g. phenethylamine, 2.1 g. sodium hydroxide, and 10.5 g. 2,2,4-trichlorobutyryl chloride, there was obtained N-phenethyl-2,2,4-trichlorobutyramide as an orange oil which was used as such in the next step.

(B) 3 ,3-dichloro-1-phenethyl-2-pyrrolidinone Following a procedure similar to that described in Example 32B and using the N-phenethyl-2,2,4-trichlorobutyramide from Example 34A and 2.1 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol-water 7.9 g. 3,3dichloro-1-phenethyl-2-pyrrolidinone; M.P. 84-85 C.

EXAMPLE 35 (A) N- [3- 3-indolyl propyl] -2,2,4-trichlorobutyramide Following a procedure similar to that described in EX- ample 32A and using 6.8 g. 3-(3-indolyl)propylarnine, 3.5 g. sodium bicarbonate, and 8.2 g. 2,2,4-trichlorobutyryl chloride, there was obtained 12.5 g. N-[3-(3-indolyl) propyl]-2,2,4-trichlorobutyramide as a brown gum which was used as such in the next step.

(B) 3,3-dichloro-1- [3- (3-indolyl)propyl] -2-pyrrolidinone Following a procedure similar to that described in Example 32B and using 12.5 g. N-[3-(3-indolyl)propyl]- 2,2,4-trichlorobutyramide from Example 35A and 1.6 g. sodium hydroxide there was obtained after recrystallization from methyl alcohol 4.2 g. 3,3-dichloro-1-[3-(3-indolyl)propyl]-2-pyrrolidinone; M.P. l03105 C.

Following a procedure similar to that described in Example 32A and substituting for 4-chlorobenzylamine an equivalent amount of:

(a) 3-aminomethylindole (b) 3-(2-aminoethyl)indole (c) 3- (Z-aminol-methylethyl -4-fluoroindole (d) 3-(2-amino-2-methylethyl)-5-methoxyindole (e) 3-(2-aminoethyl)-5-benzy1oxy-2-rnethylindole (f) 3-(2-aminoethyl)'4,7-dichloroindole (g) 3-(Z-arninoethyl)-5-methylmercaptoindole (h) 3-(2-aminoethyl-7-(trifluoromethyl)indole (i) 3-(Z-aminoethyl)-5-phenoxyindole (j) 3-(2-aminoethyl)-6-dimethylaminoindole k) 3- Z-aminoethyl -4,5 ,6-trimethoxyindole (l) 3- Z-aminoethyl -2-phenethylindole (m) 3-(Z-aminoethyl-5-n-butoxyindole there can be obtained respectively, according to this invention:

(a) N- 3-indolylmethyl -2,2,4-trichlorobutyramide (b) N- [2- 3-indolyl ethyl] -2,2,4-trichlorobutyramide (c) N- [2- 4-fiuoro-3-indolyl) -2-methylethyl] -2,2,4

trichlorobutyramide (d) N-[2- (5-methoxy-3-indolyl)-1-methylethyl] -2,2,4-

ttichlorobutyramide (e) N- 2- (-benzyloxy-2-methyl-3-indolyl ethyl] -2,2,4-

trichlorobutyr amide (f) N- [2- (4,7-dichloro-3-indolyl) ethyl] -2,2,4-trichlorobutyramide (g) N- [2- S-methylmercapto-3-indolyl) ethyl] -2,2,4-

trichlorobutyramide (h) N-{2- 7- (trifluoromethyl) -3-indolyl]ethyl}-2,2,4-

trichlorobutyramide (i) N- 2- 5-phenoxy-3-indolyl) ethyl] -2,2,4-trichlorobutyramide (j) N- [2- (6-dimethylamino-3-indolyl ethyl] -2,2,4-

trichlorobutyramide (k) N- [2- (4,5 ,6-trimethoxy-3-indolyl ethyl] -2,2,4-

trichlorobutyramide (l) N- [2- 2-phenethyl-3-indolyl ethyl] -2,2,4-trichlorobutyramide (m) N- [2- (5-n-butoxy-3-indoly1) ethyl] -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 32b and substituting for N-(4-chlorobenzyl)-2,2,4- trichlorobutyramide an equivalent amount of:

(a) N- 3-indolylmethyl) -2,2,4-trichlorobutyramide (b) N-[2-( 3-indolyl) ethyl] -2,2,4-trichlorobutyramide (c) N- [2- (4-fluoro-3-indolyl -2-methylethyl] -2,2,4-trichlorobutyramide (d) N- [2- (5-methoxy-3-indolyl) -1-methylethyl] -2,2,4-

trichlorobutyramide (e) N- 2- 5 -benZyloxy-2-methyl-3-indolyl ethyl] -2,2,4-

trichlorobutyramide (f) N- [2- (4,7-dichloro-3-indolyl) ethyl] -2,2,4-trichlorobutyramide (g) N-[2-(5-methylmercapto-3-indolyl)ethyl]-2,2,4-

trichlorobutyramide (h) N-{2- 7- trifluoromethyl -3-indolyl] ethyl} -2,2,4-

trichlorobutyramide (i) N- [2- 5-phenoxy-3-indolyl) ethyl] -2,2,4-trichlorobutyramide (j) N- [2- 6-diamethylamino-3-indolyl) ethyl] -2,2,4-

trichlorobutyramide (k) N- [2- (4,5 ,6-trimethoXy-3-indolyl ethyl -2,2,4-

trichlorobutyramide (l) N- [2- 2-phenethyl-3-indolyl ethyl] -2,2,4-trichlorobutyramide (m) N- (2- 5-n-butoxy-3-indolyl ethyl] -2,2,4-trichlorobutyramide (there can be obtained respectively, according to this invention:

(a) 3 3 -dichloro-1-(3 -indolyl)methyl-2Ppyrrolidinone (b) 3 ,3 -dichlorol- 2-(3 -indolyl) ethyl] -2-pyrrolidinone (c) 3 ,3-dichloro- 1- [2- 4-fluoro-3-indolyl -2-methylethyl] -2-pyrrolidinone (d) 3 ,3-dichloro-1- [2-(5-methoxy-3-indolyl)-1-methylethyl] -2-pyrrolidinone (e) 3,3-dichloro-l- [2- S-benzyloxy-Z-methyl-3-indolyl) ethyl] -2-pyrrolidinone (f) 3 ,3-dichloro-1- [2- (4,7-dichloro-3-indolyl) ethyl] 2-pyrrolidinone (g) 3 ,3-dichloro- 1- 2- 5-methylmercapto-3 -indolyl ethyl] -2-pyrrolidinone (h) 3,3-dichlorol-{2-[7-trifiuoromethyD-3-indolyl] ethyl}- 2-pyrro'lidinone (i) 3 ,3-dichloro-1 [2- 5-phenoxy-3 -indo1yl ethyl] -2- pyrrolidinone (5) 3,3 -dichlorol-[2-(6-dimethylamino-3-indolyl)ethyl] 2-pyrrolidin one (k) 3,3-dichloro- 1- 2- (4,5 ,6-trimethoxyl-3-indolyl) ethyl] -2-pyrrolidinone (l) 3 ,3-dichloro- 1- [2- 2-phenethyl-3-indolyl ethyl] -2- pyrrolidinone m) 3 ,3-dichlorol [2- 5-n-butoxy-3-indolyl) ethyl] 2-pyrrolidinone 28 EXAMPLE 36 (A) N,N-hexamethylene-bis(2,2,4-trichlorobutyramide) To a stirred ice-cooled mixture of 11.0 g. hexamethylenediamine in 200 ml. ethylene dichloride and 8.5 g. sodium hydroxide in ml. water was added 42.0 g. 2,2,4-trichlorobutyryl chloride dropwise during one-half hour and stirring was then continued at room temperature for two hours. The mixture was diluted with Water, washed with saturated aqueous sodium bicarbonate solution, water, dilute aqueous hydrochloric acid solution, and saturated sodium chloride solution. The ethylene dichlo ride phase was separated, dried over magnesium sulfate, and evaporated to dryness to give on crystallization from hexane-ether 39.1 g. N,N'-h'examethylene-bis(2,2,4-trichlorobutyramide) M.P. 8l-82 C.

(B) 1,1-hexamethylene-bis(3,3-dichloro-2-pyrrolidinone) To a solution of 10.0 g. N,N'-hexamethylene-bis(2,2,4- trichlorobutyramide from Example 36A in 35 ml. dimethylsulfoxide was added 2.2 g. of a mixture of sodium hydride in mineral oil (52.9% sodium hydride and the mixture was stirred for one hour with occasional cooling in order to maintain the reaction at room temperature. The resulting solution was heated on a steam bath until the pH reached seven and was then poured onto ice and extracted with chloroform. The chloroform solution was evaporated to dryness to yield after recrystallization from carbon tetrachloride 4.1 g. 1,1-hexamethylene-bis(3,3- dichloro-Z-pyrrolidinone); M.P. 90.6-91.8 C. (corr.).

Following a procedure similar to that described in Example 36A and substituting for hexamethylenediamine an equivalent amount of:

(a) ethylenediamine (b) octamethylenediamine (c) dodecamethylenediamine (d) l,Z-diamino-Z-methylpropane there can be obtained respectievly, according to this inveninvention:

(a) N,N'-ethylene-bis 2,2,4-trichlorobutyramide) (b) N,N'-octamethylene-bis 2,2,4-trichlorobutyramide) (c) N,N'-dodecamethylene-bis 2,2,4-trichlorobutyramide) (d) N,N'- l l-dimethylethylene -bis 2,2,4-trichlorobutyramide) Following a procedure similar to that described in Example 36A and substituting for 2,2,4-trichlorobutyryl chloride an equivalent amount of:

(a) 4-chlorobutyryl chloride (b) S-chlorovaleryl chloride (0) 6-chlorohexanoyl chloride there can be obtained respectively:

(a) N,N'-hexamethylene-bis(4-chlorobutyrarnide) (b) N,N-hexamethylene-bis(4-chlorovaleramide) (c) N,N-hexamethylene-bis(6-chlorohexanamide) Following a procedure similar to that described in Example 36B and substituting for N,N-hexamethylenebis(2,2,4-trichlorobutyramide) an equivalent amount of:

(a) N,N'-ethylenebis(2,2,4-trichlorobutyramide) (b) N,N'-octamethylene-bis 2,2,4-trichlorobutyramide) (c) N,N'-dodecamethylene-bis(2,2,4-trichlorobutyrarnide) (d) N,N'-( 1,1-dimethylethylene)-bis(2,2,4-trichlorobutyramide) (e) N,N-hexamethylene-bis(4-chlorobutyramide) (f) N,N-hexamethylene-bis(5-chlorovaleramide) (g) N,N'-hexamethylene-bis(6-chlorohexanamide) azepin-Z-one EXAMPLE 37 (A) N,N'-(4-xyly1ene)bis(2,2,4-trichlorobutyramide) T o a stirred, ice-cooled mixture of 6.8 g. 4-xylylenediamine in 200 ml. ethylene dichloride and 4.2 g. sodium hydroxide in 100 ml. water was added 21 g. of 2,2,4-trichlorobutyryl chloride dropwise during fifteen minutes and stirring was continuedfor one-half hour. The resulting precipitate was collected by filtration and washed with water. The filtrate was washed with dilute aqueous hydrochloric acid solution and water, dried over sodium sulfate, and evaporated to dryness to yield, after combination with the crop obtained by filtration followed by trituration in ether-hexane, N,N'-(4-xylylene)bis(2,2,4- trichlorobutyramide); M.P. 9398 C.

(B) 1,1 -(4xylylene) bis (3,3-dichloro-2-pyrrolidinone) To a stirred solution of the N,N-(4-xylylene)bis(2,2,4- trichlorobutyramide), from Example 37A, in 200 ml. ethyl alcohol was added a solution of 4.2 g. sodium hydroxide in 42 ml. water. Stirring was continued for ten minutes and dilute aqueous hydrochloric acid solution was added until the solution turned acidic, followed by 300 ml. water. The resulting crystals were filtered to give after recrystallization from chloroform-hexane 4.9 g. 1,1- (4-xylylene)bis(3,3-dichloro 2 pyrrolidinone); M.P. 219.2222.0 C. (dec.) (corr.).

Following a procedure similar to that described in Example 37A and substituting for 4-xylylenediamine an equivalent amount of:

(a) 2-xylylenediamine (b) 3-xylylenediamine 0) 2,2'- (4-phenylene bis (ethylamine) (d) 2,2-(3-phenylene)bis(ethylamine) (e) 2,2'- Z-phenylene bis ethylamine) f 2,2- 2,5-dimethyl-4-phenylene) bis ethylamine) (g) 5-tert-butyl-3-xylylenediamine (h) 2,4,6-trimethyl-3-xylylenediamine (i) 4-methoxy-6-methyl-3-xylylenediamine (j) a,a'-dimethyl-4-xylylenediamine (k) 2,5-dimethoxy-4-xylylenediamine l) 2,2'- (4-phenylene bis l-methylethylamine) there can be obtained respectively, according to this in vention:

(a) N,N'- 2-xylylene bis 2,2,4-trichlorobutyramide) (b) N,N- 3-xylylene bis 2,2,4-trichlorobutyramide) (c) N,N- 2,2'- (4-phenylene bisethyl] bis (2,2,4-trichlorobutyramide) d) N,N'- 2,2'- 3-phenylene bisethyl] bis 2,2,4-trichlorobutyramide) (e) N,N'-[2,2-(2-phenylene)bisethyllbis(2,2,4-trichlorobutyramide) (f) N,N- 2,2- 2,5 -dimethyl-4-phenylene bisethyl] bis (2,2,4-trichlorobutyramide) (g) N,N- 5-tert-butyl-3-xylylene bis 2,2,4-trichlorobutyramide) (h) N,N'-(2,4,6-trimethyl-3-xylylene)bis(2,2,4-trichlorobutyramide) (i) N,N'-(4-methoxy-6-methyl-3-xyly1ene)bis(2,2,4-

trichlorobutyramide) (j) N,N- a,a'-dimethyl-4-xylylene bis (2,2,4-trichlorobutyramide) (k) N,N-(2,5-dimethoxy-4-xylylene)bis(2,2,4-trichlorobutyramide) (l) N,N-[2,2'- (4-phenylene)bis l-methylethyl) ]bis (2,2,4-trichlorobutyramide) Following a procedure similar to that described in Example 37A and substituting for 2,2,4-trichlorobutyryl chloride an equivalent amount of:

(a) 4-chlorobutyryl chloride (b) S-chlorovaleryl chloride (c) 6-chlorohexanoyl chloride there can be obtained respectively:

(a) N,N- (4-xy1ylene bis 4-chlorobutyramide) (b) N,N'- 4-xylylene bis S-chlorovaleramide) (c) N,N- (4-xylylene bis 6-chlorohex-anamide) Following a procedure similar to that described in Example 37B and substituting for N,N'-(4-xylylene)bis (2,2,4-trichlorobutyramide) an equivalent amount of:

(a) N,N'- 2-xylylene bis 2,2,4-trichlorobutyramide) b) N,N- 3-xylylene) bis 2,2,4-trichlorobutyramide) c) N,N-[2,2- (4-phenylene bisethyl] bis (2,2,4-trichlorobutyramide) (d) N,N- [2,2'- 3-phenylene bisethyl] bis 2,2,4-trichlorobutyramide) (e) N,N 2,2'- Z-phenylene bisethyl] bis 2,2,4-trichlorobutyramide) (f) N,N- [2,2'- 2,5 -dimethyl-4-phenylene bisethyl] bis (2,2,4-trichlorobutyramide) (g) N,N- 5-tert-butyl-3-xylylene bis (2,2,4-trichl0robutyramide) (h) N,N'- 2,4,6-trimethyl-3-xylylene bis 2,2,4-trichlorobutyramide) (i) N,N'- (4-methoxy-6-methyl-3-xylylene bis( 2,2,4-

triclilorobutyramide) (j) N,N'- u,ot'-dimethyl-4-xylylene bis 2,2,4-trichlorobutyramide) (k) N,N- (2,5 -dimethoxy-4-xylylene) bis 2,2,4-trichlorobutyramide) (1) N,N'- [2,2- (4-phenylene bis( l-methylethyl) Ibis 2,2,4-trichlorobutyramide) (m) N,N- (4-xylylene bis 4-chlorobutyramide) (n) N,N- 4-xylylene bis S-chlorovaleramide) (o) N,N'- 4-xylylene bis 6-chlorohexanamide) there can be obtained respectively, according to this invention:

(a) l, 1 2-xylylene bis 3 ,3-dichloro-Z-pyrrolidinone) b 1,1'-(3-xylylene)bis(3,3-dichl0ro-2-pyrrolidin0ne) (c) 1, 1 2,2- 4-pheny1ene bisethyl] bis 3,3-dichloro- 2-pyrrolidinone) d) 1,1-[2,2'-(3-phenylene)bisethyl]bis(3,3-dichloro-2- pyrrolidinone) (e) 1,1- [2,2'- (Z-phenylene) bisethyl]-bis(3,3-dichloro- 2-pyrrolidinone) (f) 1, l [2,2'- 2,5 -dimethyl-4-phenylene) bisethyl] bis (3 ,3-dichloro-2-pyrrolidinone) (g) 1, 1 (5-tert-butyl-3-xylylene bis 3,3-dichloro-2- pyrrolidinone) (h) 1, 1 -(2,4,6-trimethyl-3-xylylene) bis (3,3 -dichloro-2- pyrrolidinone) (i) 1, 1 (4-methoxy-6-methyl-3 -xylylene bis 3 ,3-dichloro-Z-pyrrolidinone) (j) 1, 1 a,a-dimethyl-4-xylylene bis 3,3-dichloro-2- pyrrolidinone) k) 1, 1'- 2,5 -dimethoXy-4-xylylene bis 3 ,3-dichloro-2- pyrrolidinone) (l) 1 1 [2,2- (4-phenylene) bis l-methylethyl 1 bis (3 ,3-

dichloro-Z-pyrrolidinone) (m) 1,1 -(4-xylylene)bis(2-pyrrolidinone) (n) 1,1'-(4-xylylene)bis(2-piperidone) o) 1, 1 4-xylylene bis (hexahydro-2H-azepin-2-one) Following the general procedure hereinbefore described for the chlorination of a 2-oxopolymethylenimine and using the following:

(a) 1 1 (4-xy1ylene bis Z-pyrrolidinone) (b) 1, 1 (4-xylylene) bis (Z-piperidone (c) 1,1-(4-xylylene)bis(hexahydro-ZH-azepin-Z-one) there can be obtained respectively:

(a) 1, 1 4-xylylene) bis 3 ,3-dichloro-2-pyrrolidinone) (b) 1, 1'- (4-xylylene) bis (3 ,3-dichloro-2-piperidone) c) 1,1'-(4-xylylene)'bis(3,3-dichlor0hexahydro-2H- azepin-Z-one) EXAMPLE 3 8 (A) 'N,N'- (2-chloro-1,4-phenylene) bis (2,2,4- trichlorobutyramide) To a stirred, ice-cooled mixture of 6.02 g. Z-chloro- 1,4-phenylenediamine in 150 ml, benzene and 6.15 g. sodium carbonate in 100 ml. water was added a solution of 11.5 g. 2,2,4-trichlorobutyryl chloride in 30 ml. benzene dropwise during twenty minutes and stirring was continued with cooling for fifteen minutes and at room temperature for one and one-half hours. The benzene layer was separated and washed with water, 0.5 N aqueous hydrochloric acid solution, water, 5% aqueous sodium bicarbonate solution, and Water, dried over calcium sulfate and evaporated to dryness to yield on crystallization from hexane 8.33 g. N,N'-(Z-chloro-l,4-phenylene)bis- (2,2,4-trichlorobutyramide); M.P. 90.0-91.5 C.

(B) 1, 1'-(2-chloro-1,4-phenylene) bis (3 ,3-dichloro-2- pyrrolidinone) To a stirred mixture of 9.77 g. N,N'-(2-chloro-1,4- phenylene)bis(2,2,4-trichlorobutyramide) in 75 ml. ethyl alcohol was added 0.8 g. sodium hydroxide in 10 ml.

Water. When the pH of the mixture returned to seven another 0.8 g. sodium hydroxide in 10 ml. water was added and when the pH returned to seven it was adjusted to approximately thirteen by the addition of 50% aqueous sodium hydroxide solution. The mixture was diluted with water and the precipitate was filtered and washed with water to yield after recrystallization from acetone-hexane 5.8 g. 1,1'-(2-chloro 1,4 pheny1enc)bis( 3,3-dichlro-2- pyrrolidinone); M.P. 240-242" C. (dec.).

Following a procedure similar to that described in Example 38A and substituting for 2-chloro-1,4-phenylenediamine an equivalent amount of:

(a) 1,2-phenylenediamine (b) 1,3-phenylenediamine (c) 1,4-phenylenediamine (d) 3 ,4-di (trifluoromethyl) -1,2-phenylenediamine (e) -brorno-3,4-dimethyl-1,2-phenylenediamine (f) 3,6-di-n-butoxy-1,2-phenylenediamine (g) 4-n-butyl-1,2-phenylenediamine (h) 4-tert-butyl-1,2-phenylenedi'amine (i) 4,5-dich1oro-1,2-pheny1enediamine (j) 4,6-diethylsulfonyl-1,3-phenylenediamine (k) 4,6-diethylmercapto-1,3-phenylenediamine (l) 4,5-dimethoxy-1,3-phenylenediamine 32 (m) 2,6-dinitro-4-methoxy-1,3-phenylenediamine (n) 2,5-diethoxy-1,4-phenylenediamine (o) 2-chloro-6-methoxy-1,4-phenylenediamine there can be obtained respectively, according to this invention:

(a) N,N'- 1,2-phenylene)bis 2,2,4-trich1orobutyramide) (b) N,N'-(1,3-phenylene)bis(2,2,4-trichlorobutyramide) (c) N,N'-( 1 ,4-phenylene bis 2,2,4-trichloro'butyramide) (d) N,N' 3,4-di (trifluoromethyl) 1,2-phenylene] bis- (2,2,4-trichlorobutyramide) (e) N,N'- 5-brorno-3,4-dimethyl-1,2-phenylene) bis- (2,2,4-trichlorobutyramide) (f) N,N'- 3 ,6-di-n-butoxy- 1 ,2-phenylene bis (2,2,4-

trichlorobutyramide) (g) N,N- 4-n-butyl- 1 ,Z-phenylene bis (2,2,4-trichlorobutyramide) (h) N,'N-(4-tert-butyl-1,2-pheny1ene)bis(2,2,4-trichlorobutyramide) (i) N,N'- (4,5 -dichloro- 1 ,Z-phenylene bis 2,2,4-trichlorobutyramide) (j) N,N- 4,6-diethylsulfonyl- 1 3-phenylene) bis (2,2,4-

trichlorobutyramide) (k) N,N-(4,-6-diethylmercapto-1,3-phenylene) bis(2,2,4-

trichlorobutyramide) (l) N,N'- 4,5 -dimethoxy- 1,3-phenylene) bis (2,2,4-trichlorobutyramide) m) N,N'-(2,6-dinitro-4-methoxy-1,3-phenylene)bis- (2,2,4-trichlorobutyramide) (n) N,N- (2,5-diethoxy- 1 ,4-phenylene bis 2,2,4-trichlorobutyramide) (o) N,N'-(2-chloro-6-methoxy-1,4-phenylene)bis(2,2,4-

trichlorobutyramide) By following a procedure similar to that described in Example 38A and substituting for 2,2,4-trichlorobutyryl chloride an equivalent amount of (a) 4-chlorobutyryl chloride (b) 5-chlorova1eryl chloride (c) 6-chlorohexanoyl chloride there can be obtained respectively:

(a) N,N'- 2-chloro- 1 ,4-phenylene) bis (4-chlorobutyramide) (b) N,N'-(2-chloro-1,4-phenylene)bis(S-chlorovaleramide) (c) N,-N- 2-chloro- 1 ,4-phenylene bis 6-chlorohexanamide) Following a procedure similar to that described in Example 38B and substituting for N,N' (2 chloro 1,4- phenylene) bis( 2,2,4-trichlorobutyramide) an equivalent amount of:

(a) N,N-( 1,2-phenylene bis 2,2,4-trichlorobutyramide) (b) N,N-( 1,3-phenylene bis 2,2,4-trichlorobutyramide) c) N,N-( 1,4-phenylene bis 2,2,4-trichlorobutyramide) (d) N,N- [3 ,4-di(trifluoromethyl) -1,2-phenylene] bis- (2,2,4-trichlorobutyramide) (e) N,N'- 5-bromo-3 ,4-dimethyl-1,2-phenylene)bis- 2,2,4-trichlorobutyramide) (f) N,N'- (3 ,6-di-n-butoxy-1,2-phenylene) bis (2,2,4-trichlorobutyramide) (g) N,N-(4-n-butyl-1,2-phenylene) bis (2,2,4-trichlorobutyramide) (h) N,N-(4-tert-butyl-1,2-phenylene)bis(2,2,4-trichlorobutyramide) (i) N,N-(4,5-dichloro-1,2-phenylene)bis(2,2,4-trichlorobutyramide) (j) N,N- 4,6-diethylsulfonyl- 1 ,3-phenylene bis 2,2,4-

trichlorobutyramide) '(k) N,N'- (4,6-diethylmercapto- 1 ,3-phenylene bis 2,2,4-

trichlorobutyramide) (l) N,N'- (4,5-dimethoxy- 1 ,3-phenylene) bis (2,2,4-trichlorobutyramide) (m) 'N,N- (2,6-dinitro-4-methoxy-1,3-phenylene)bis- 2,2,4-trichlorobutyramide (n) N,N-(2,5-diethoxy-1,4-phenylene)bis(2,2,4-trichlorobutyramide) o) N,N'-(2-chloro-6-methoxy- 1,4-phenylene) bis (2,2,4-

trichlorobutyramide) (p) N,N'- (2-chloro-1,4-phenylene)bis (4-chloroblltyramide) (q) N,N'-(2-chloro-1,4-phenylene) bis (S-chlorovaleramide) (r) N,N'- 2-chloro- 1 ,4-phenylene )bis ('6-chlorohexanamide) there can be obtained respectively, according to this invention:

(a) 1,1-( 1,2-phenylene bis 3 ,3-dichloro-2-pyrrolidinone) (b) 1, 1 1,3-phenylene bis 3 ,3-dich1oro-2-pyrrolidinone) (c) 1, 1'-( 1,4-phenylene bis 3,3-dichloro-2-pyrrolidinone) (d) 1,-1- [3 ,4-di(trifiuoromethy1)-1,2-phenylene]bis(3 ,3

dichloro-Z-pyrrolidinone) (e) 1,1 '-(5-bromo-3,4-dimethyl-1,2-phenylene)bis(3 ,3-

dichloro-2-pyrrolidinone) (f) 1 1 3,6-di-n-butoxy- 1,2-phenylene bis 3 ,3-dichloro- 2-pyrrolidinone) (g) 1, 1 4-n-butyl- 1 ,Z-phenylene bis 3,3-dichloro-2- pyrrolidinone) (h) 1, 1'- 4-tert-butyl-1 ,2-phenylene bis 3, 3-dichloro-2- pyrrolidinone) (i) 1, 1 4,5 -dichloro- 1 ,Z-phenylene bis( 3,3-dichloro-2- pyrrolidinone) (j) 1, l (4,6-diethylsulfonyl- 1 ,3-phenylene bis( 3,3 -dichloro-2-pyrrolidinone) (k) 1, 1 4,6-diethylmerc-apto- 1 ,3-phenylene bis 3,3-dichloro-2-pyrrolidinone) (l) 1, l 4,5 -dimethoxy- 1 ,3-phenylene bis 3,3-dichloro- 2-pyrrolidinone) (m) 1,1'-(2,6-dinitro-4-methoxy-1,3-phenylene)bis(3 ,3

dichloro-Z-pyrrolidinone) (n) 1, 1 (2,5 -diethoxy- 1 ,4-phenylene bis 3,3 -dichloro- 2-pyrrolidinone) (o) 1,1-(2-chloro-6-methoxy-1,4-phenylene)bis(3,3-dichloro-2-pyrrolidinone) (p) 1, 1'- (2-chloro- 1 ,4-phenylene bis (2-pyrrolidinone) (q) 1, 1 2-chloro-1 ,4-phenylene bis (2-piperidone) (r) 1,1-(2-chloro-1,4-phenylene)bis(hexahydro-ZH-azepin-2-one) Following the general procedure hereinbefore described for the chlorination of a 2-oxopolyme'thylenimine and using the following:

(a) 1, l 2-ehloro- 1 ,4-phenylene bis 2-pyrrolidonone) (b) 1,1-(2-cl1loro-1,4-phenylene)bis(2-piperidone (c) 1,1-(2-ch1oro-1,4-phenylene)bis(hexahydro-ZH- azepin-2-one) there can be obtained respectively:

(a) 1,1-(2-chloro-1,4-phenylene)bis(3,3-dichloro-2- pyrrolidinone) (b) 1,1'-(2-chloro-1,4-phenylene)bis(3,3-dichloro-2- piperidone) (c) 1,1'-(2-chloro-1,4-phenylene)bis(3,3-dichlorohexahydro-2H-azepin-2-one) EXAMPLE 39 (A) N,N'-(4-chloro-1,3-phenylene)bis(2,2,4-trichlorobutyramide) Following a procedure similar to that described in Example 38A and using 7.12 g. 4-chl0ro-1,3-phenylenediamine, 11.24 g. sodium carbonate, and 21.0 g. 2,2,4-trichlorobutyryl chloride, there was obtained after crystallization from hexane 20.7 g. N,N-(4-chloro-1,3-phenylene)bis(2,2,4-trichlorobutyramide); M.P. 90.592.0 C.

34 (B) 1,1-(4-chloro-1,3-phenylene)bis(3,3-dichloro-2- pyrrolidinone) Following a procedure similar to that described in Example 38B and using 17.15 g. N,N-(4-chlor0-1,3phenylene)bis(2,2,4-trichlorobutyramide) from Example 39A and 2.8 g. sodium hydroxide there was obtained after recrystallization from methyl alcohol 11.1 g. 1,l'-(4- chloro 1,3 phenylene)bis(3,3-dichloro 2 pyrrolidinone); M.P. 154-155 C.

EXAMPLE 40 (A) N,N- (4-chloro-1,2-phenylene)bis (2,2,4-trichlorobutyramide) Following a procedure similar to that described in Example 38A and using 7.13 g. 4-chloro-1,2-phenylenediamine, 5.62 g. sodium carbonate, and 21.0 g. 2,2,4-trichlorobutyryl chloride, there was obtained 19.0 g. N,N- (4 chloro-l,2-phenylene)bis(2,2,4-trichlorobutyramide) as crystals.

(B) 1,1-(4-chloro-1,2-phenylene)bis(3 ,3 -dichloro-2- pyrrolidinone) Following a procedure similar to that described in Example 38B and using 11.8 g. N,N'-(4-chloro-1,2-phenylene)bis(2,2,4-trichlorobutyramide) from Example 40A and 3.88 g. sodium hydroxide, there was obtained after recrystallization from methyl alcohol 8.22 g. 1,1-(4- chloro-1,2-phenylene)bis(3,3 dichloro-Z-pyrrolidinone); M.P. 228-229 C.

EXAMPLE 41 (A) N,N'- 3,3 -dichloro-4,4'-biphenylylene bis 2,2,4- trichlorobutyramide) To a stirred mixture of 6.33 g. 3,3'-dichloro-4,4'-biphenyldiamine in 200 ml. benzene and 5.62 sodium carbonate in 60 ml. water, cooled to 10 C., was added a solution of 10.5 g. 2,2,4-trichlorobutyryl chloride in 50 ml. benzene dropwise during twenty minutes and stirring was continued twenty minutes at 10 to 15 C. and one and one-half hours at room temperature. The benzene phase was separated, washed with water, saturated aqueous sodium bicarbonate solution, water, 1 N aqueous hydrochloric acid solution and water, dried over calcium sulfate, and evaporated to dryness to yield N,N-(3,3'-dichloro-4,4'-biphenylylene)bis (2,2,4 trichlorobutyramide) as a viscous oil which was used as such in the next step.

(B) 1,1'-) 3,3-dich1oro-4-4,'-biphenylylene)bis(3,3- dichloro-Z-pyrrolidinone) To a stirred mixture of the N,N'-(3,3'-dichloro-4,4'- biphenylylene)bis(2,2,4-trichlorobutyramide) from Example 41A in ml. ethyl alcohol was added a solution of 1.0 g. sodium hydroxide in 20 ml. water an when the pH returned to seven another solution of 1.0 g. sodium hydroxide in 20 ml. water was added and finally the pH was adjusted to approximately thirteen by the addition of a few drops of 50% aqueous sodium hydroxide solution. The mixture was diluted with water and the resulting precipitate was filtered to yield after recrystallization successively from acetone and chloroform 5.07 g. l,1'-(3,3'-dichl0ro 4,4 biphenylene)bis(3,3-dichloro- Z-pyrrolidinone); M.P. 265-266" C. (dec.).

Following a procedure similar to that described in Example 41A and substituting for 3,3-dichloro-4,4'-biphenyldiamine an equivalent amount of:

(a) 2,2-biphenyldiamine (b) 2,3'-biphenyldiamine (c) 2,4-biphenyldiamine (d) 3,3'-biphenyldiamine (e) 3,4-biphenyldiamine (f) 4,4-biphenyldiamine (g) 3,3'-dihexyloxy-4,4'-bipheny1diamine (h) 4,5-dinitro-2,2'-biphenyldiamine (i) 5-chloro-2,4'-biphenyldiamine (j) 2,2,4,4',6,6'-hexamethyl-3,3'-biphenyldiamine (k) 4,4'-di(trifluoromethyl)-2,2'-biphenyldiamine (l) 2',5,6'-tribr0m0-6-iodo-3,4'-biphenyldiamine (m) 4,4-dimethylmercapto-3,3-biphenyldiamine (n) 2,2-dich1oro-5,5'-dietl1oxy-4,4'-biphenyldiamine (o) 3,3-diethyl-4,4-biphenyldiamine (p) 3,3'-diphenethyloXy-4,4-biphenyldiamine (q) 3,3'-diphenoxy-4,4'-biphenyldiamine (r) 3-methylsulf0nyl-4,4'-biphenyldiamine (s) 3,5-dibromo-4-nitro-2,4'-biphenyldiarnine there can be obtained respectively, according to this invention:

(a) N,N'- 2,2-biphenylylene bis (2,2,4-trichlorobutyramide) (b) N ,N'- 2,3 biphenylylene bis( 2,2,4-trichlorobutyramide) (c) N,N- (2,4-biphenylyle1ie bis 2,2,4-trichlorobutyramide) (d) N,N'- (3 ,3 -biphenylylene bis 2,2,4-trichlorobuyramide) (e) N,N- 3,4-biphenylylene bis (2,2,4-trich1or0butyramide) (f N,N'- (4,4'-biphenylylene bis 2,2,4-trichlorobutyramide) (g) N,N-(3,3'-dihexyloxy-4,4'-bipheny1y1ene)bis(2,2,4-

trichlorobutyramide) h) N,N- 4,5 '-dinitro-2,2'-biphenylylene bis (2,2,4-

trichlorobutyramide) (i) N ,N'- 5 -chlro-2,4-biphenylylene bis 2,2,4-

trichlorobutyramide) (j) N,N'-( 2,2',4,4,6,6hexamethyl-3,3-biphenylene bis- (2,2,4-trichlorobutyramide) I (k) N,N-[4,4-di(trifluoromethy1)2,2-biphenylylene] bis 2,2,4-trichlorobutyramide) (1) N,N'- 2',5,6-tribromo-6-iodo-3 ,4-biphenylylene) bis- 2,2,4-trichlor0butyramide) m) N,N- 4,4-dimethylmercapto-3, 3'-biphenylylene) bis 2,2,4-trichlorobutyramide) n) N,N'- 2,2'-dichloro-5 ,5 -diethoxy-4,4'-biphenylylene) bis 2,2,4-trichlorobutyramide) o) N,N'- 3 ,3 '-diethyl-4,4-biphenylylene bis (2,2,4-

trichlorobutyramide) (p) N,N- 3,3 '-diphenethyloxy-4,4'-biphenylylene bis- 2,2,4-trichlorobutyramide) (q) N,N- (3 ,3 '-diphenoxy-4,4'-biphenylylene bis 2,2,4-

trichlorobutyramide) (r) N,N- (3 -methylsulfonyl-4,4-biphenylylene bis- (2,2,4-trichlorobutyramide) (s) N,N- (3 ',5 '-dibromo-4-nitro-2,4'-biphenylylene) bis 2,2,4-trichlorobutyramide) Following a procedure similar to that described in 'Example 41A and substituting for 2,2,4-trichlorobutyryl chloride an equivalent amount of:

(a) 4-ch1orobutyryl chloride (b) S-chlorovaleryl chloride (c) 6-chloroheXanoyl chloride there can be obtained respectively (a) N,N'- 3 ,3 '-dichloro-4,4'-biphenylylene bis 4- chlorobutyramide) (b) N,N'- 3 ,3 -dichloro-4,4'-biphenyly1ene bis 5- chlorovaleramide) (c) N,N'- (3 ,3-dich1oro-4,4'-biphenylylene bis 6- chlorohexanamide) Following a procedure similar to that described in Example 418 and substituting for N,N'-(3,3'-dichloro' 4,4'-biphenylene)bis(2,2,4-trichlorobutyramide) an equivalent amount of:

(a) N,N' 2,2-biphenylylene) bis 2,2,4-trichlorobutyramide) (b) N,N'- 2,3'-biphenylylene) bis 2,2,4-trichlorobutyramide) (c) N,N'- 2,4'-biphenylylene bis 2,2,4-trichlorobutyramide) (d) N,N'- 3 ,3 '-biphenylylene bis 2,2,4-trichlorobutyramide) (e) N,N'- 3,4-biphenylylene bis (2,2,4-trichl0robutyramide) (f) N,N'- 4,4'-biphenylylene bis 2,2,4-trichl0robuyramide) (g) N,N- 3 ,3 '-dihexyloxy-4,4'-biphenylylene bis (2,2,4-

trichlorobutyramide) (h) N,N- (4,5 '-dinitro-2,2'-biphenylylene bis (2,2,4-

trichlorobutyramide) (i) N,N'- S-chloro-2,4-biphenyly1ene bis 2,2,4-

trichlorobutyramide) (j) N,N'-(2,2',4,4,6,6-hexamethyl-3,3'-biphenyly1ene) bis 2,2,4-trichlorobutyramide) (k) N,N [4,4'-di (trifluoromethyl -2,2'-biphenylylene] bis 2,2,4-trichlorobutyramide) (l) N,N-(2,5,6'-tribromo-6-iodo-3,4'-biphenylylene) bis 2,2,4-trichlorobutyramide) (In) N,N'- (4,4'dimethylmercapto-3,3 '-biphenylylene) bis 2,2,4trich10robutyramide) n) N,N'- 2,2'-dichloro-5 ,5 -dieth0Xy-4,4-bi phenylylene bis 2,2,4-trichlorobutyramide) o) N,N- 3,3 '-diethyl-4,4'-biphenylylene bis 2,2,4-

trichlorobutyramide) (P) N,N'- (3,3 '-diphenethyloxy-4,4'biphenylylene bis- 2,2,4-trichlorobutyramide) (q) N,N'- 3 ,3 '-diphenoxy-4,4'-bipheny1ylene bis 2,2,4-

trichlorobutyramide) (r) N,N'- 3 -methylsulfonyl-4,4'-biphenylylene bis- 2,2,4-trichlorobutyramide) (s) N,N'- 3 ,5 '-dibromo-4-nitro-2,4'-biphenylylene bis- (2,2,4-trichlorobutyramide) (t) N,N- 3 ,3 '-dichlor0-4,4-biphenylylene bis 4- chlorobutyramide) (u) N,N'- 3 ,3 -dichloro-4,4'-biphenylylene bis 5- chlorovaleramide) v) N,N- 3 ,3 -dichl0ro-4,4'-biphenylylene bis 6- chlorohexanamide) there can be obtained respectively, according to this invention:

(a) 1,1 '-(2,2'-biphenylylene)bis(3, 3-dichloro-2- pyrrolidinone) (b) 1, 1 2,3 -biphenylylene) bis 3,3-dichloro-2- pyrrolidinone) (c) 1, 1 2,4-bipheny1ylene bis 3 ,3-dichloro-2- pyrrolidinone) (d) 1,1'-(3 ,3'-biphenylylene bis 3,3-dichl0ro-2- pyrrolidinone) (e) 1 1 (3 ,4-biphenylylene bis 3,3-dichloro-2- pyrrolidinone) (f) 1,1'- (4,4'-biphenylylene bis 3,3-dichloro-2- pyrrolidinone) (g) 1, 1'- (3 ,3 -diheXy1oxy-4,4'-biphenylylene bis 3,3-

dichloro-Z-pyrrolidinone) (h) 1 1- 4,5 -dinitro-2,2-biphenylylene bis 3 ,3-

dichloro-Z-pyrrolidinone) (i) 1, 1 5-chloro-2,4'-biphenylylene) bis 3,3-dichloro- Z-pyrrolidinone) (l) 1,1-(2,2,4,4'-6,6-hexamethyl-3,3'-biphenylylene) bis 3,3-dichloro-2-pyrrolidinone) (k) 1 ,1- (4,4'-di(trifluoromethyl)-2,2-bipheny1y1ene) bis(3,3-dichloro-2-pyrrolidinone) (l) 1,1'-(2',5,6-tribr0mo-6-iodo-3,4'-biphenylylene) bis 3,3-dichloro-2-pyrrolidinone) m) 1,1- (4,4-dimethylmercapto-3 ,3'biphenylene bis- (3 ,3-dichloro-2-pyrrolidinone) (n) 1 1 2,2'-dichloro-5 ,5 '-diethoXy-4,4-biphenylylene) bis 3 ,3 -dichloro-2-pyrolidinone) (0) 1, 1- 3 ,3 -diethyl-4,4-biphenylylene bis 3 3-dichl0ro- 2-pyrrolidinone) (p) 1 1 3 ,3 '-diphenethyloxy-4,4-biphenylylene bis 3 ,3-

dichloro-2-pyrrolidinone) (q) (3,3 -diphenoxy-4,4'-biphenylylene bis 3 ,3-dichloro- Z-pyrrolidinone) (r) 1, 1'(3-methylsulfonyl-4,4'-biphenylene) bis (3 ,3-

dichloro-2-pyrrolidinone) (s) 1 ,1'-(3 ',5'-di-bromo-4-nitro-2,4'-biphenylylene bis 3,3-dichloro-Z-pyrrolidinone) (t) 1, 1 (3 ,3'-dichloro-4,4-biphenylylene bis 2-pyrrolidinone) (u) 1,1 3 ,3 '-dichloro-4,4'-biphenylylene) bis 2- piperidone) (v) 1,1'- 3 ,3 -dichloro-4,4'-biphenylylene) bis (hexahydro-2H-azepin-2-one) Following the general procedure hereinbefore described for the chlorination of a 2-oxopolymethylenimine and using the following:

(a) 1,1-(3,3'-dichloro-4,4-biphenylylene)bis(2-pyrrolidinone) (b) 1,1'-(3,3-dichloro-4,4'-biphenylylene)bis(2-piperidone) 1,1'-(3,3'-dichloro-4,4-biphenylylene)bis(hexa hydro-2H-azepin-2-one) there can be obtained:

(a) 1,1-(3,3-dichloro-4,4'-biphenylylene)bis(3,3-dichloro-2-pyrrolidinone) (h) 1,1-(3,3'-dichloro-4,4-biphenylylene)bis(3,3-dichloro-2-piperidone) (c) 1,1'-(3,3'-dichloro-4,4-biphenylylene)bis(3,3-dichlorohexahydro-2H-aZepin-2-one) EXAMPLE 42 (A) N-(2,6-dimethyl-4-pyrimidyl)-2,2,4-trichlorobutramide To a stirred solution of 15.0 g. 4-amino-2,6-dimethylpyrimidine in 500 ml. ethylene dichloride and 13.0 g. sodium carbonate in 100 ml. water, at room temperature, was added 26 g. 2,2,4-trichlorobutyryl chloride in 50 ml. ethylene dichloride dropwise during fortyfive minutes and stirring was continued for four and one-half hours. The ethylene dichloride layer was separated, washed with water, dried over sodium sulfate, and evaporated to dryness to yield 22 g. of N-(2,6-dimethyl-4-pyrimidyl)-2,2,4' trichlorobutyramide as a yellow oil which was used as such in the next step.

(B) 3,3-dichloro-1-(2,6-dimethyl-4-pyrirnidyl)-2- I pyrrolidinone To a stirred ice-cooled solution of 20 g. N1(2,6-di methyl-4-pyrimidyl) 2,2,4 trichlorobutyramide, from Example 42A, in 200 ml. methyl alcohol was added a solution of 2.4 g. sodium hydroxide in 10 ml. water and stirring was continued for one hour. The mixture was evaporated to a small volume and extracted with ethylene dichloride. The extract was washed with water, dried over sodium sulfate and evaporated to dryness to yield, after trituration with cold ether and recrystallization from methyl alcohol-water and ether-hexane, 5.98 g. 3,3-dichloro-1-(2,6-dimethyl-4-pyrimidyl) 2 pyrrolidinone; M.P. 99100 C.

Following a procedure similar to that described in Example 42A and substituting for 4-amino-2,6-dimethyl pyrimidine an equivalent amount of:

' (a) 2-aminopyrimidine (b) 4-aminopyrimidine (c) S-aminopyrimidine (d) 4-amino-5-bromo-6-chloro-2-methylmercaptopyrimidine (e) 5-amino-2,4-bis(dimethylamino)pyrimidine (f) 4-arnino-2-n-butyl-6-chloro-S-nitropyrimidine (g) 4amino-6- (trifluoromethyl) pyrimidine (h) 2-amino-S-benzyl-4-chloropyrimidine 3-8 (i) 5-amino-2,4-diphenoxypyrimidine (j) 4-amino-2-ethylsulfonyl-S-methylpyrimidine (k) 2-amino-5-n-butoxypyrimidine (l) 5-amino-4-chloro-6-rnethoxy-2-methylpyrimidine (m) 4-amino-5-hexyl-2-propylpyrimidine (n) Z-acetamido-S-aminopyrimidine there can be obtained respectively, according to this invention:

(a) N- 2-pyrimidyl -2,2,4-trichlorobutyramide (b) N- 4-pyrimidyl -2,2,4-trichlorobutyramide (c) N-( 5-pyrimidyl -2,2,4-trichlorobutyramide (d) N- S-bromo-6-chloro-2-methylmercapto-4-pyrimidyl -2,2,4-trichlorobutylramide (e N- [2,4-bis (di'methylamino -5-pyrimidyl -2,2,4-trichlorobutyramide (it) N- 2-n-butyl-6-chloro-5-nitro-4-pyrimidyl) -2,2,4-

trichlorobutyramide (g) N- [6- trifluoromethyl -4-pyrimidyl] -2,2,4-trichloro butyramide (h) N- 5-benyl-4-chloro-2-pyrimidyl -2,2,4-trichloro butyramide (i) N-(2,4-diphenoxy-S-pyrimidyl)-2,2,4-trichlorobutyramide (j) N-(2-ethylsulfonyl-5-methyl-4-pyrimidyl)-2,2,4-

trichlorobutyramide (k) N- 5-n-but0xy-2-pyrimidyl -2,2,4-trichlorobutyramide (l) N- 4-chloro-6-methoxy-2-methyl-S-pyrimidyl -2,2,4-

trichlorobutyramide (m) N 5-hexy1-2-propyl-4-pyrimidyl -2,2,4-trichlor0- butyramide (n) N-(2-acetamido-5-pyrimidyl -2,2,4-trichlorobutyramide Following a procedure similar to that described in Example 42B and substituting for N-(2,6-dimethyl-4- pyrimidyl) 2,2,4 trichlorobutyramide an equivalent amount of:

there can be obtained respectively, according to this in vention:

(a) 3,3-dichloro- 1- (Z-pyrimidyl -2-pyrrolidinone (b) 3 ,3-dichloro- 1- 4-pyrimidyl) -2-pyrrolidinone (c) 3 ,3-dichloro- 1- 5-pyrimidyl -2-pyrrolidinone (d) 3 ,3-dichloro- 1- S-bromo- 6-chlor0-2-methylmercapto- 4-pyrimidyl -2-pyrro1idinone (e) 3 ,3-dichloro- 1- [2,4-bis (dimethylamino -5-pyrimidyl]2-pyrrolidinone By treating 3,3-dichloro-l-(Z-acetamido-S-pyrimidyl)- 9 2-pyrrolidinone in absolute ethyl alcohol, at room temperature, with an ethereal solution containing an amount of hydrogen chloride slightly in excess of that required to hydrolyze the acetamido group, there can be obtained the hydrochloride salt of 3,3-dichloro-1-(2-amino-5-pyrimidyl)-2-pyrrolidinone which can be converted to the free base by dissolving the salt in ethyl alcohol and treating the resulting solution with an equivalent amount of sodium carbonate in water.

EXAMPLE 43 (A) N- (4-chlorophenyl) -5-chlorovaleramide To a stirred ice-cooled solution of 51 g. 4-chloroaniline and 45.1 g. triethylamine in 1300 ml. dry methylene dichloride was added a solution of 68.8 g. 5-chlorovaleryl chloride in 200 ml. dry methylene dichloride dropwise during one hour and stirring was continued one hour with cooling and one hour at room temperature. The resulting solution was washed with water, saturated :aqueous sodium bicarbonate solution and water, dried over anhydrous calcium sulfate and evaporated to dryness under reduced pressure to give after recrystallization from ethyl acetatehexane 91.9 g. N- (4-chlorophenyl)-5-chlorovaleramide; M. P. 109.5-110 C.

(B) N- (4-chlorophenyl -2-piperidone To a solution of 24.6 g. N-(4-chlorophenyl)-5-ch1orovaleramide in 250 ml. ethyl alcohol Was added 40 ml. of an aqueous solution containing 4 g. sodium hydroxide as follows: initially ml. of solution was added and when the reaction solution became neutralanother 10 ml. of solution was added. Finally When the reaction solution again became neutral ml. of solution was added, stirring was continued for three hours and the resulting mixture was filtered and the filtrate was evaporated to dryness under reduced pressure. The residue was taken up in ether, the mixture was filtered and the filtrate was evaporated to dryness to give after recrystallization from hexane 18.6 g. N-(4-chlorophenyl)-2-piperidone; M.P. 69.5-70.5 C.

(C) 3,3-dichloro-N-(4-chlorophenyl)-2-piperidone To a stirred slurry of 31.24 g. phosphorus pentachloride in 100 ml. xylene at room temperature was added a solution of 10.48 g. N-(4-chlorophenyl)-2-piperidone in 75 ml. xylene dropwise during twenty-five minutes. The mixture was slowly heated to 89 during forty-five minutes, heating was continued one-half hour, and the mixture was evaporated to dryness under reduced pressure and the residue was stirred with 400 ml. 10% aqueous sodium carbonate and ice. The resulting solid was collected by filtration to give after recrystallization from and charcoal treatment in methanol 8.05 g. 3,3-dichloro-N-(4-chlorophenyl)-2-piperidone; M.P. 145146.5 C.

40 EXAMPLE 44 (A) N- (4fiuorophenyl -5-chlorovaleramide Following a procedure similar to that described in Example 43A and using 11.11 g. 4-fluoroaniline and 12.65 g. triethylamine in 340 ml. dry methylene dichloride and 17.04 g. 5-chlorovaleryl chloride in 220 ml. dry methylene dichloride there was obtained after recrystallization from ethyl acetate-hexane 19.12 g. N-(4-fiuorophenyl)-5-chlorovaleramide; H.P. 81.5-83" C.

(B) N- (4-fiuorophenyl) -2-piperidone Following a procedure similar to that described in Example 43B and using 11.48 g. N-(4-fiuorophenyl)-4- chlorovaleramide in ml. ethyl alcohol and 25 ml. of an aqueous solution containing 2 g. sodium hydroxide there was obtained after recrystallization from hexane 6.35 g. N-(4-fluorophenyl)-2-piperidone; M.P. 102104 C.

(C) 3,3-dichloro-N-(4-fiuorophenyl)-2-piperidone Following a procedure similar to that described in Example 43C and using 31.3 g. phosphorus pentachloride in 100 ml. xylene and 9.66 g. of N-(4-fluorophenyl)-2- piperidone in ml. xylene there was obtained after recrystallization from methanol 7.04 g. 3,3-dichloro-N- (4-fluorophenyl)-2-piperidone; M.P. 140.514l.5 C.

EXAMPLE 45 (A) N-(4-bromophenyl)-5-chlorovaleramide Following a procedure similar to that described in Example 43A and using 8.6 g. 4-bromoaniline and 6.06 g. triethylamine in 300 ml. dry methylene dichloride and 8.52 g. 5-chlorovaleryl chloride in ml. dry methylene dichloride there was obtained after recrystallization from ethyl acetate-hexane 11.65 g. N-(4-bromophenyl)-5-chlorovaleramide; M.P. 100-101 C.

(B) N- (4-bromophenyl) -2-piperidone Following a procedure similar to that described in Example 43B and using 14.53 g. N-(4-bromophenyl)-4- chlorovaleramide in 175 ml. ethyl alcohol and 10 ml. of an aqueous solution containing 2 g. sodium hydroxide there was obtained after recrystallization from hexane 11.02 g. N-(4-bromophenyl)-2-piperidone; M.P. 78.5- 80 C.

(C) 3,3-dichloro-N-(4-bromophenyl)-2-piperidone Following a procedure similar to that described in Example 43C and using 13.9 g. phosphorus pentachloride in 100 ml. xylene and 5.66 g. N-(4-bromophenyl)-2-piperidone in ml. xylene there was obtained after recrystallization from methanol and ethyl acetate-hexane 2.48 g. 3,3-dichloro-N-(4-bromophenyl)-2-piperidone; M.P. 15 9- 160.6 C.

EXAMPLE 46 (A) N- [4-chloro-2- (trifluoromethyl) phenyl] 5-chlorovaleramide Following a procedure similar to that described in Example 43A and using 19.56 g. 4-chloro-2-(trifluoromethyl)-aniline and 12.2 g. triethylamine in 400 ml. dry methylene dichloride and 17.04 g. S-chlorovaleryl chloride in 250 ml. dry methylene dichloride there was obtained after recrystallization from ethyl acetate-hexane 16.6 g. N- [4-chloro-2- (trifluoromethyl phenyl] -5-chlorovaleramide; M.P. 109-111 C.

(B) N- [4-chloro-2- trifluoromethyl phenyl] -2-piperidone Following a procedure similar to that described in Example 43B and using 11 g. N-[4-chloro-2-(trifluoromethyl)-phenyl]-5-chlorovaleramide in 100 ml. ethyl alcohol and 10 ml. of an aqueous solution containing 1.10 g. sodium hydroxide there was obtained after recrystallization from hexane 6.38 g. N-[4-chloro-2-(trifluoromethyl) phenyl]-Z-piperidone; M.P. 78.580 C. 

